Process for making triazine UV absorbers using lewis acids and reaction promoters

ABSTRACT

It has been now surprisingly discovered after extensive research that 2-halo-4,6-bisaryl-1,3,5-triazine can be prepared with unprecedented selectivity, efficiency, mild conditions, and in high yield by the reaction of cyanuric halide with aromatics in the presence of at least one Lewis acid and at least one reaction promoter. This reaction is also unprecedently general as a variety of aromatics can be used to produce a wide selection of 2-halo-4,6-bisaryl-1,3,5-triazines. The novel approach includes the use of the reaction promoters in combination with at least one Lewis acid under certain reaction conditions to promote the formation of 2-halo-4,6-bisaryl-1,3,5-triazine compounds from cyanuric halide. Preferably, the Lewis acids and reaction promoters are combined to form a complex. 2-Halo-4,6-bisaryl-1,3,5-triazines are key intermediates for making 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazine class of UV absorbers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 09/779,597, filedFeb. 9, 2001 now U.S. Pat. No. 6,730,785, allowed; which is a divisionalof U.S. Ser. No. 09/442,000, filed Nov. 17, 1999, now U.S. Pat. No.6,486,316 B1; which claims benefit of U.S. Provisional Application No.60/108,786, filed Nov. 17, 1998.

FIELD OF THE INVENTION

This invention relates to a novel, highly efficient and general processfor making 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazines class oftrisaryl-1,3,5-triazine UV absorbers and their precursors,2-halo-4,6-bisaryl-1,3,5-triazines, from cyanuric halide. Morespecifically, the invention relates to a novel process for the synthesisof triazine compounds in the presence of a reaction facilitatorcomprising at least one Lewis acid and at least one reaction promoter.The process includes the reaction of a cyanuric halide with substitutedor unsubstituted aromatic compounds to produce2-halo-4,6-bisaryl-1,3,5-triazine compounds. This process produceshalo-bisaryl-1,3,5-triazine compounds in higher yields than are possibleusing present methods. The triazine compounds that are produced areprecursors of triazine UV absorbers which are used to stabilize organicmaterials against damage by light, heat, oxygen, or other environmentalforces. The process of producing such UV absorbers can be carried outstep-wise or continuously in an one-pot reaction process.

BACKGROUND OF THE INVENTION

Triazine UV absorbers are an important class of organic compounds whichhave a wide variety of applications. One of the most important areas ofapplications is to protect and stabilize organic materials such asplastics, polymers, coating materials, and photographic recordingmaterial against damage by light, heat, oxygen, or environmental forces.Other areas of applications include cosmetics, fibers, dyes, etc.

Triazine derived UV absorbers are a class of compounds that typicallyinclude at least one 2-oxyaryl substituent on the 1,3,5-triazine ring.Triazine based UV absorber compounds having aromatic substituents at the2-, 4-, and 6-positions of the 1,3,5-triazine ring and having at leastone of the aromatic rings substituted at the ortho position with ahydroxyl group or blocked hydroxyl group are generally preferredcompounds.

In general this class of triazine UV absorber compounds is well known inthe art. Disclosures of a number of such trisaryl-1,3,5-triazines can befound in the following U.S. patents, all of which are incorporated byreference as fully set forth herein: U.S. Pat. Nos. 3,118,887;3,242,175; 3,244,708; 3,249,608; 3,268,474; 3,423,360; 3,444,164;3,843,371; 4,619,956; 4,740,542; 4,775,707; 4,826,978; 4,831,068;4,962,142; 5,030,731; 5,059,647; 5,071,981; 5,084,570; 5,106,891;5,185,445; 5,189,084; 5,198,498; 5,288,778; 5,298,067; 5,300,414;5,323,868; 5,354,794; 5,364,749; 5,369,140; 5,410,048; 5,412,008;5,420,008; 5,420,204; 5,461,151; 5,476,937; 5,478,935; 5,489,503;5,543,518; 5,538,840; 5,545,836; 5,563,224; 5,575,958; 5,591,850;5,597,854; 5,612,084; 5,637,706; 5,648,488; 5,672,704; 5,675,004;5,681,955; 5,686,233; 5,705,643; 5,726,309; 5,726,310; 5,741,905; and5,760,111.

A preferred class of trisaryltriazine UV absorbers (UVAs) are based on2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazines, i.e., compounds withtwo non-phenolic aromatic groups and one phenolic aromatic groupadvantageously derived from resorcinol. The 4-hydroxyl group of theparent compounds, 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazines, aregenerally functionalized to make2-(2-hydroxy-4-alkoxyaryl)-4,6-bisaryl-1,3,5-triazine compounds for enduse.

A number of commercial products exist in which the para-hydroxyl groupof the phenolic ring is functionalized and the non-phenolic aromaticrings are either unsubstituted phenyl (e.g., Tinuvin® 1577) or m-xylyl(e.g. Cyasorb® UV-1164, Cyasorb® UV-1164L, Tinuvin® 400, and CGL-1545).These UV absorbers are preferred because they exhibit high inherentlight stability and permanence compared to other classes of UV absorberssuch as benzotriazole and benzophenone compounds.

There are several processes known in the literature for the preparationof triazine based UV absorbers. (See, H. Brunetti and C. E. Luethi,Helvetica Chimica Acta, 1972, 55, 1566-1595, S. Tanimoto et al., Senryoto Yakahin, 1995, 40(120), 325-339).

A majority of the approaches consist of three stages. The first stage,the synthesis of the key intermediate,2-chloro-4,6-bisaryl-1,3,5-triazine, from commercially availablematerials can involve single or multi-step processes. Thereafter in thesecond stage, 2-chloro-4,6-bisaryl-1,3,5-triazine is subsequentlyarylated with 1,3-dihydroxybenzene (resorcinol) or a substituted1,3-dihydroxybenzene in the presence of a Lewis acid to form the parentcompound 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. The parentcompound 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine, as mentionedabove, maybe further functionalized, e.g., alkylated, to make a finalproduct 2-(2-hydroxy-4-alkoxyaryl)-4,6-bisaryl-1,3,5-triazine.

There have been several approaches reported in the literature on thesynthesis of the key intermediate 2-chloro-4,6-bisaryl-1,3,5-triazine.Many of these approaches utilize cyanuric chloride, a readily availableand inexpensive starting material. For example, cyanuric chloride isallowed to react with aromatics (ArH, such as m-xylene) in the presenceof aluminum chloride (Friedel-Crafts reaction) to form2-chloro-4,6-bisaryl-1,3,5-triazine, which is allowed to react in asubsequent step with resorcinol to form2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazine (See, U.S. Pat. No.3,244,708). There are several limitations to this process, viz., thereaction of cyanuric chloride with aromatics is not selective and leadsto a mixture of mono-, bis-, and tris-arylated products includingunreacted cyanuric chloride (See, Scheme 1). The desired product,2-chloro-4,6-bisaryl-1,3,5-triazine, must be isolated by crystallizationor other purification methods before further reaction.

Another major drawback of the above mentioned process is that thereaction of cyanuric chloride with aromatics is not generally applicableto all aromatics. It is well known in the literature that the processprovides a useful yield of the desired intermediate,2-chloro-4,6-bisaryl-1,3,5-triazine, only when m-xylene is the aromaticreagent (GB 884802). With other aromatics, an inseparable mixture ofmono-, bis-, and trisaryl products are formed with no selectivity forthe desired 2-chloro-4,6-bisaryl-1,3,5-triazine (See, H. Brunetti and C.E. Luethi, Helvetica Chimica Acta, 1972, 55, 1575; and S. Tanimoto andM. Yamagata, Senryo to Takahin, 1995, 40(12), 325-339). U.S. Pat. No.5,726,310 describes the synthesis of m-xylene based products.2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine is first synthesizedand without isolation allowed to react with resorcinol in a one-pot,two-step process to produce2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,which is subsequently purified by crystallization. A one pot process forpreparing asymmetric tris-aryl-1,3,5-triazines from cyanuric chloride aswell as from mono-aryl-dichloro triazines was earlier described in U.S.Pat. No. 3,268,474.

Several approaches were developed in an attempt to solve the abovementioned problems related to the formation of the key intermediate2-chloro-4,6-bisaryl-1,3,5-triazine from cyanuric chloride. For example,cyanuric chloride is allowed to react with an aryl magnesium halide(Grignard reagent), to prepare 2-chloro-4,6-bisaryl-1,3,5-triazine (See,Ostrogovich, Chemiker-Zeitung, 1912, 78, 738; Von R. Hirt, H. Nideckerand R. Berchtold, Helvetica Chimica Acta, 1950, 33, 365; U.S. Pat. No.4,092,466). This intermediate after isolation can be subsequentlyreacted in the second step with resorcinol to make a2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazine (See, Scheme 2). Thisapproach does not selectively synthesize2-chloro-4,6-bisaryl-1,3,5-triazine; the mono- and tris-arylatedproducts are formed in significant amounts (See, H. Brunetti and C. E.Luethi, Helvetica Chimica Acta, 1972, 55, 1575). Modifications withbetter results have been reported (See, U.S. Pat. No. 5,438,138).Additionally, the modified process is not suitable for industrial scaleproduction and is not economically attractive.

Alternate approaches were developed to solve the selectivity problemwhen synthesizing 2-chloro-4,6-bisaryl-1,3,5-triazine using either aFriedel-Crafts reaction or Grignard reagents, however, all solutionsrequired additional synthetic steps. One approach, is outlined in Scheme3. In the first step, cyanuric chloride is allowed to react with 1equivalent of an aliphatic alcohol to make in high selectivity amonoalkoxy-bischlorotriazine. In the second step,monoalkoxy-bischlorotriazine was allowed to react with aromatics in thepresence of aluminum chloride to prepare intermediatesmonoalkoxy/hydroxy-bisaryltriazines. These intermediates were thenconverted to 2-chloro-4,6-bisarayl-1,3,5-triazines in the third step byreaction with thionyl chloride or PCl₅. In the fourth step,2-chloro-4,6-bisaryl-1,3,5-triazines were allowed to react withresorcinol to synthesize2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazines. In the aboveprocess, the desired product was formed with high selectivity. However,the two additional

steps required made the process less attractive economically as anindustrial process.

A similar approach is outlined in Scheme 4 (See, U.S. Pat. Nos.5,106,972 and 5,084,570). The main difference is that cyanuric chloridewas first allowed to react with 1 equivalent of alkanethiol, instead ofan alcohol. As with the process summarized in Scheme 3, additional stepswere required, making the process neither efficient nor economicallyfeasible.

Recent improvements are disclosed in European patent application0,779,280 A1 and Japanese patent application 09-059263.

Other approaches do not utilize cyanuric chloride as a startingmaterial. For example, the synthesis of2-chloro-4,6-bisaryl-1,3,5-triazine as disclosed in EP 0497734 A1 and asoutlined in Scheme 5. In this process benzamidine hydrochloride is firstallow to react with a chloroformate and the resulting product is thendimerized. The resulting 2-hydroxy-4,6-bisaryl-1,3,5-triazine isconverted to 2-chloro-4,6-bisaryl-1,3,5-triazine by treatment withthionyl chloride, which is subsequently allowed to react with resorcinolto synthesize 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazine, asshown in Scheme 5.

An alternate approach for the preparation of2-chloro-4,6-bisaryl-1,3,5-triazines is based on the reaction of arylnitrites with phosgene in the presence of HCl in a sealed tube (S.Yanagida, H. Hayama, M. Yokoe, and S. Komori, J. Org. Chem., 1969, 34,4125. Another approach is the reaction of N,N-dimethylbenzamide withphosphoryl chloride complex which is then allowed to react withN-cyanobenzamidine to form 2-chloro-4,6-bisaryl-1,3,5-triazine (R. L. N.Harris, Synthesis, 1990, 841). Yet another approach involves thereaction of polychloroazalkenes, obtained from the high temperature ofchlorination of amines, with amidines to form2-chloro-4,6-bisaryl-1,3,5-triazines (H. G. Schmelzer, E. Degener and H.Holtschmidt, Angew. Chem. Internat. Ed., 1966, 5, 960; DE 1178437). Noneof these approaches are economically attractive, and thus are notcommercially feasible.

Finally, there are at least three approaches which do not require theintermediacy of 2-chloro-4,6-bisaryl-1,3,5-triazine for the preparationof the parent compound,2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. These approachesutilize benzonitriles or benzamidines as starting materials (See U.S.Pat. Nos. 5,705,643 and 5,478,935; WO 96/28431). The benzamidines arecondensed with 2,4-dihydroxybenzaldehyde followed by aromatization(Scheme 6) or condensed with phenyl/alkyl 2,4-dihydroxybenzoates (Scheme7) or 2-aryl-1,3-benzoxazine-4-ones (Scheme 8) to form2-(2,4,-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. These approaches havethe drawback that the starting materials are expensive and may requireadditional steps to prepare. Moreover, overall yields are notsatisfactory and the processes are not economically attractive.

Based on Benzamidine reactions with 2,4-dihydroxybenzaldehyde:

In summary, although direct Lewis acid catalyzed bisarylation ofcyanuric chloride to form the desired2-chloro-4,6-bisaryl-1,3,5-triazine intermediate is the mosteconomically attractive approach, this process has found only limiteduse due to the following problems:

-   1. Poor selectivity: Almost total lack of selectivity for    bisarylation (with the exception of m-xylene where some selectivity    is observed). Mono- and tris-arylated triazines are the major    by-products.-   2. Poor reactivity: Typical reaction conditions require high    temperatures, long reaction times, and variable temperatures during    the course of reaction. Aromatics with electron-withdrawing groups    (such as chlorobenzene) fail to react beyond mono-substitution even    at elevated temperatures and long reaction times.-   3. Safety hazards: Temperature and addition rate must be carefully    monitored to avoid an uncontrollable exotherm which may result in    safety hazards.-   4. Poor process conditions: The reaction slurry is either thick and    difficult to stir or solid thereby making stirring impossible. The    process requires various reaction temperatures and addition of    reactants in portions over several hours.-   5. Isolation problem/poor isolated yield: Separation and    purification of the desired product is difficult and isolated yields    are generally poor and commercially unacceptable.-   6. Not a general process: The reaction cannot be used with different    aromatics other than m-xylene.

Thus, there remains a need for improved methods for synthesizingtriazine UV absorbers.

SUMMARY OF THE INVENTION

It has been now surprisingly discovered after extensive research that2-halo-4,6-bisaryl-1,3,5-triazine can be prepared with unprecedentedselectivity, efficiency, mild conditions, and in high yield by thereaction of cyanuric halide with aromatics in the presence of a reactionfacilitator comprising at least one Lewis acid and at least one reactionpromoter. This reaction is also unprecedently general as a variety ofaromatics can be used to produce a wide selection of2-halo-4,6-bisaryl-1,3,5-triazines. The novel approach includes the useof the reaction promoter in combination with at least one Lewis acidunder certain reaction conditions to promote the formation of2-halo-4,6-bisaryl-1,3,5-triazine compounds from cyanuric halide.Preferably, the Lewis acids and reaction promoters are combined to forma reaction facilitator in the form of a complex.

The present invention specifically relates to a process for thesynthesis of a triazine compound by reacting a cyanuric halide ofFormula V:

with at least one substituted or unsubstituted aromatic compound such asa compound of Formula II:

wherein R₆, R₇, R₈, R₉, and R₁₀ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbonatoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbon atoms including substituted or unsubstitutedbiphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO₂R, SO₃H, SO₃M, wherein Mis an alkali metal, R and R′ are the same or different and each ishydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms,acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, oraracyl of 6 to 24 carbons atoms, and optionally with either of R₆ andR₇, R₇ and R₈, R₈ and R₉, or R₉ and R₁₀, taken tog being a part of asaturated or unsaturated fused carbocyclic ring optionally containing O,N, or S atoms in the ring, with the reaction being conducted in thepresence of at least one reaction facilitator comprising at least oneLewis acid and at least one reaction promoter, optionally in an inertsolvent, for a sufficient time at a suitable temperature and pressure toproduce a triazine compound of Formula III:

wherein X is a halogen and Ar₁ and Ar₂ are the same or different andeach may be the radical of a compound of Formula II:

In a further embodiment, the triazine compound of Formula III is furtherreacted with a compound of Formula IV:

wherein R₁, R₂, R₃, R₄, and R₅ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbons atoms, substituted or unsubstitutedbiphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′,OCOR, CN, SR, SO₂R, SO₃H, SO₃M, wherein M is an alkali metal, R and R′are the same or different and each is hydrogen, alkyl of 1 to 24 carbonatoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms,optionally with either of R₃ and R₄, or R₄ and R₅, taken together beinga part of a saturated or unsaturated fused carbocyclic ring optionallycontaining O, N, or S atoms in the ring, and Y is a direct bond, O, NR″,or SR″ wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkylof 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally in thepresence of an additional Lewis acid, additional reaction promoter, oradditional reaction facilitator, for a sufficient time at a suitabletemperature and pressure, optionally in the presence of an inertsolvent, to produce a compound of Formula I:

The reaction to form the compound of Formula III and the reaction toform the compound of Formula I can be carried out without isolating thecompound of Formula III.

Another embodiment relates to a process for synthesizing a triazinecompound of Formula I:

wherein Ar₁ and Ar₂ are the same or different, and each independently isa radical of a compound of Formula II:

wherein R₆, R₇, R₉, R₉, and R₁₀ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbonatoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbon atoms including substituted or unsubstitutedbiphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO₂R, SO₃H, SO₃M, wherein Mis an alkali metal, R and R′ are the same or different and each ishydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms,acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, oraracyl of 6 to 24 carbons atoms, and optionally with either of R₆ andR₇, R₇ and R₈, R₈ and R₉, or R₉ and R₁₀, taken tog being a part of asaturated or unsaturated fused carbocyclic ring optionally containing O,N, or S atoms in the ring, which comprises:

simultaneously reacting in the presence of a reaction facilitatorcomprising at least one Lewis acid and at least one reaction promoter,sufficient amounts of a cyanuric halide of Formula V:

where each X is independently a halide such as fluorine, chlorine,bromine or iodine, with a compound of Formula IV:

wherein R₁, R₂, R₃, R₄, and R₅ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbons atoms, substituted or unsubstitutedbiphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′,OCOR, CN, SR, SO₂R, SO₃H, SO₃M, wherein M is an alkali metal, R and R′are the same or different and each is hydrogen, alkyl of 1 to 24 carbonatoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms,optionally with either of R₃ and R₄, or R₄ and R₅, taken together beinga part of a saturated or unsaturated fused carbocyclic ring optionallycontaining O, N, or S atoms in the ring, and Y is a direct bond, O, NR″,or SR″ wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkylof 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24carbon atoms, or aracyl of 6 to 24 carbons atoms, and a compound ofFormula II:

for a sufficient time, at a suitable temperature and pressure to formthe compound of Formula I.

Another embodiment relates to a process for synthesizing a triazinecompound of Formula I:

wherein Ar₁ and Ar₂ are the same or different, and each independently isa radical of a compound of Formula II:

wherein R₆, R₇, R₈, R₉, and R₁₀ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbonatoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbon atoms including substituted or unsubstitutedbiphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO₂R, SO₃H, SO₃M, wherein Mis an alkali metal, R and R′ are the same or different and each ishydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms,acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, oraracyl of 6 to 24 carbons atoms, and optionally with either of R₆ andR₇, R₇ and R₈, R₈ and R₉, or R₉ and R₁₀, taken tog being a part of asaturated or unsaturated fused carbocyclic ring optionally containing O,N, or S atoms in the ring, which comprises:

reacting in the presence of a reaction facilitator comprising at leastone Lewis acid and at least one reaction promoter, sufficient amounts ofa compound of Formula III:

wherein X is independently a halide such as fluorine, chlorine, bromineor iodine and Ar₁ and Ar₂ are the same or different and each is aradical of a compound of Formula II; with a compound of Formula IV:

wherein R₁, R₂, R₃, R₄, and R₅ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbons atoms, substituted or unsubstitutedbiphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′,OCOR, CN, SR, SO₂R, SO₃H, SO₃M, wherein M is an alkali metal, R and R′are the same or different and each is hydrogen, alkyl of 1 to 24 carbonatoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms,optionally with either of R₃ and R₄, or R₄ and R₅, taken together beinga part of a saturated or unsaturated fused carbocyclic ring optionallycontaining O, N, or S atoms in the ring, and Y is a direct bond, O, NR″,or SR″ wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkylof 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24carbon atoms, or aracyl of 6 to 24 carbons atoms, for a sufficient time,at a suitable temperature and pressure to form the compound of FormulaI.

DETAILED DESCRIPTION OF THE INVENTION

The present inventors have found that by using a combination comprisingof at least one Lewis acid and at least one reaction promoter,preferably combined to form a reaction facilitator, the reaction of acyanuric halide with substituted or unsubstituted aromatic compounds canprepare triazine derived 2-halo-4,6-bisaryl-1,3,5-triazine compounds inhigher yield, with higher selectivity, at a lower reaction temperature,and/or within shorter reaction times than previously known.

Even more surprising is the fact that the reaction facilitator has beenused with excellent results. This approach is in stark contrast to thestate of the prior art where the use of anhydrous Lewis acids alone hasalways been advocated for this reaction step. It has also beendiscovered that 2-halo-4,6-bisaryl-1,3,5-triazines of this invention canbe further reacted, without isolation, with a variety of phenolicderivatives to form 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazine.Furthermore, the reaction can be applied to a variety of aromaticcompounds. The key reasons for the increase in selectivity andreactivity has been shown to be the use of the reaction promoter.

As used herein, the cyanuric halide is a compound of the Formula V:

where each X is independently a halide such as fluorine, chlorine,bromine, or iodine.

The term aromatic compound is to include compounds of the Formula II:

wherein R₆, R₇, R₈, R₉, and R₁₀ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbonatoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbon atoms including substituted or unsubstitutedbiphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO₂R, SO₃H, SO₃M, wherein Mis an alkali metal, R and R′ are the same or different and each ishydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms,acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, oraracyl of 6 to 24 carbons atoms, and optionally with either of R₆ andR₇, R₇ and R₈, R₈ and R₉, or R₉ and R₁₀, taken tog being a part of asaturated or unsaturated fused carbocyclic ring optionally containing O,N, or S atoms in the ring.

Preferred aromatic compounds include benzene, toluene, ethylbenzene,m-xylene, o-xylene, p-xylene, chlorobenzene, dichlorobenzene,mesitylene, isobutylbenzene, isopropylbenzene, m-diisopropyl benzene,tetralin, biphenyl, naphthalene, acetophenone, benzophenone,acetanilide, anisole, thioanisole, resorcinol, bishexyloxy resorcinol,bisoctyloxy resorcinol, m-hexyloxy phenol, m-octyloxy phenol, or amixture thereof.

The term “phenolic compound” is to include compounds of the formula IV:

wherein R₁, R₂, R₃, R₄, and R₅ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbons atoms, substituted or unsubstitutedbiphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′,OCOR, CN, SR, SO₂R, SO₃H, SO₃M, wherein M is an alkali metal, R and R′are the same or different and each is hydrogen, alkyl of 1 to 24 carbonatoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms,alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms,cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms,aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms,optionally with either of R₃ and R₄, or R₄ and R₅, taken together beinga part of a saturated or unsaturated fused carbocyclic ring optionallycontaining O, N, or S atoms in the ring, and Y is a direct bond, O, NR″,or SR″ wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkylof 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24carbon atoms, or aracyl of 6 to 24 carbons atoms.

Preferred phenolic compounds are substituted or unsubstitutedmonohydroxybenzene, monalkoxybenzene, dihydroxybenzene, dialkoxybenzene,hydroxyalkoxybenzene, trihydroxybenzene, trialkoxybenzene,hydroxybisalkoxybenzene, and bishydroxyalkoxybenzene. More preferredphenolic compounds are: resorcinol (1,3-dihydroxybenzene); C-alkylatedresorcinols, e.g., 4-hexylresorcinol; mono-O-alkylated resorcinols,e.g., 3-methoxyphenol, 3-octyloxyphenol, 3-hexyloxyphenol, etc.;di-O-alkylated resorcinols, e.g., 1,3-dimethoxybenzene,1,3-dioctylbenzene, 1,3-dihexyloxybenzene; C-alkylated-di-O-alkylatedresorcinols, e.g., 4-hexyl-1,3-dimethoxybenzene; other polyhydroxy,polyalkoxy, hydroxy-alkoxy aromatics, e.g., 1,3,5-trihydroxybenzene,1,3,5-trialkoxybenzene, 1,4-dihydroxybenzene, 1-hydroxy-4-alkoxybenzene,or mixtures thereof.

The term “Lewis acid” is intended to include aluminum halides,alkylaluminum halides, boron halides, tin halides, titanium halides,lead halides, zinc halides, iron halides, gallium halides, arsenichalide, copper halides, cadmium halides, mercury halides, antimonyhalides, thallium halides, zirconium halides, tungsten halides,molybdenum halides, niobium halides, and the like. Preferred Lewis acidsinclude aluminum trichloride, aluminum tribromide, trimethylaluminum,boron trifluoride, boron trichloride, zinc dichloride, titaniumtetrachloride, tin dichloride, tin tetrachloride, ferric chloride, or amixture thereof.

As used herein the term “reaction promoter” is understood to comprise acompound which is used in combination with the Lewis acid to facilitatethe reaction. Thus, triazine compounds are produced at lower reactiontemperatures, greater yields, or higher selectivities compared to theuse of the Lewis acid alone. Suitable reaction promoters include acids,bases, water, alcohols, aliphatic halides, halide salts, acid halides,halogens, alkenes, alkynes, ester, anhydride, carbonate, urethane,carbonyl, epoxy, ether, acetal compounds, or mixtures thereof.

Suitable alcohol compounds include carbon compounds of C₁-C₂₀, straightchain or branched, saturated or unsaturated, cyclic or non-cyclic,aromatic or non-aromatic, which has at least one hydroxyl group andwhich optionally contains at least one halide, thiol, thiol ether,amines, carbonyl, esters, carboxylic acids, amide, etc. Suitablyalcohols include methanol, ethanol, propanol, butanol, isobutanol,t-butanol, 1,2-ethanediol, 3-chloro-1-propanol, 2-hydroxyl-acetic acid,1-hydroxyl-3-pentanone, cyclohexanol, cyclohexenol, glycerol, phenol,m-hydroxyl-anisole, p-hydroxyl-benzylamine, benzyl alcohol, etc.

Suitable acid compounds include any inorganic or organic acid thatcontains at least one acidic proton, which may or may not be dissolvedin an aqueous or organic solution. The organic acids include any organiccompound that contains at least one acidic functional group includingRCO₂H, RSO₃H, RSO₂H, RSH, ROH, RPO₃H, RPO₂H, wherein R is as definedabove. Preferred protic acids include HCl, HBr, H₁, HNO₃, HNO₂, H₂S,H₂SO₄, H₃PO₄, H₂CO₃, acetic acid, formic acid, proprionic acid, butanoicacid, benzoic acid, phthalic acid, oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, methanesulfonic acid, andp-toluenesulfonic acid or mixtures thereof.

Suitable aliphatic halides include C₁-C₂₀ hydrocarbon compounds,saturated or unsaturated, cyclic or non-cyclic, aromatic ornon-aromatic, that are substituted with at least one halide. Optionally,the aliphatic halide may be substituted in one or more positions with anhydroxyl, an ether, a polyether, a thiol, a thioether, an amine, such as—NHR, —NR′₂, —NRR′, a carboxylic acid, an ester, an amide or a carbonstructure of C₁-C₂₀ group which may be saturated or unsaturated andcyclic or non-cyclic, aromatic and which optionally may be substitutedwith any of the above preceding groups or mixtures thereof.

Specific aliphatic halide compounds that are suitable include carbontetrachloride, chloroform, methylene chloride, chloromethane, carbontetrabromide, tert-butylchloride, bromoform, dibromomethane,bromomethane, diiodomethane, iodomethane, dichloroethane, dibromoethane,chloroethanol, bromoethanol, benzyl chloride, benzyl bromide,ethanolamine, chloroacetic acid, bromoacetic acid or mixtures thereof.

The bases that are suitable include inorganic or organic bases dissolvedeither in water, an organic solvent, or a mixture of solvents. Inorganicbases include LiOH, NaOH, KOH, Mg(OH)₂, Ca(OH)₂, Zn(OH)₂, Al(OH)₃,NH₄OH, Li₂CO₃, Na₂CO₃, K₂CO₃, MgCO₃, CaCO₃, ZnCO₃, (Al)₃(CO₃)₂,(NH₄)₃CO₃, LiNH₂, NaNH₂, KNH₂, Mg(NH₂)₂, Ca(NH₂)₂, Zn(NH₂)₂, Al(NH₂)₃,or a mixture thereof. Organic bases include hydrocarbon compounds withC₁-C₉ cyclic or non-cyclic that contain at least one alkoxide, amine,amide, carboxylate, or thiolate and which may be substituted in one ormore positions with a halide, an hydroxyl, an ether, a polyether, athiol, a thioether, an amine, such as —NHR, —NR′₂, —NRR′, a carboxylicacid, an ester, or an amide. Organic bases include CH₃O⁻, CH₃CH₂O⁻,CH₃CH₂CH₂O⁻, (CH₃)₂CHO⁻, ((CH₃)₂CH)₂CHO⁻, CH₃CH₂CH₂CH₂O⁻, (CH₃)₃CO⁻,CH₃NH₂, CH₃CH₂NH₂, CH₃CH₂CH₂NH₂, (CH₃)₂CHNH₂, ((CH₃)₂CH)₂CHN₂,CH₃CH₂CH₂CH₂NH₂, (CH₃)₃CNH₂, (CH₃)₂NH, (CH₃CH₂)₂NH, (CH₃CH₂CH₂)₂NH,((CH₃)₃CH)₂)NH, (((CH₃)₂CH)₂CH)₂NH, (CH₃CH₂CH₂CH₂)₂NH, ((CH₃)₃C)₂NH,(CH₃CH₂)₃N, (CH₃CH₂CH₂)₃N, ((CH₃)₂CH)₃N, (((CH₃)₂CH)₂CH)₃N,(CH₃CH₂CH₂CH₂)₃N, ((CH₃)₃C)₃N, CH₃NH⁻, CH₃CH₂NH⁻, CH₃CH₂CH₂NH⁻,(CH₃)₂CHNH⁻, ((CH₃)₂CH)₂CHNH⁻, CH₃CH₂CH₂CH₂NH⁻, (CH₃)₃CNH⁻, (CH₃)₂N⁻,(CH₃CH₂)₂N⁻, (CH₃CH₂CH₂)₂N⁻, ((CH₃)₂CH)₂N⁻, (((CH₃)₂CH)₂CH)₂N⁻,(CH₃CH₂CH₂CH₂)₂N⁻, ((CH₃)₃C)₂)₂N⁻, pyrrolidine, piperidine, pyrrole,pyridine, aniline, tetramethylenediamine, the corresponding deprotonatedamine, and a cation were appropriate. Organic bases also includes saltsof deprotonated carboxylic acids such as salts of formate, acetate,propylate, butanoate, benzoate, with Li, Na, K, Mg, Ca, Al, Zn, or anyother suitable cation. Organic base includes mixtures of theaforementioned inorganic and organic bases, or a mixture thereof.

Halogen reaction promoters include fluorine, chlorine, bromine, iodine,or mixed halogens dissolved in either water, an organic solvent, or amixture of solvents or present as part of an organic or inorganiccompound. Halogenated solvents that are suitable includedichloromethane, chloroform, carbon tetrachloride, dibromomethane,bromoform, iodomethane, diiodomethane, dichloroethane,1,1,2,2-tetrachloroethane, benzene, toluene, acetone, acetic acid,hexane, or a mixture thereof.

Additional reaction promoters that are suitable include hydrocarboncompounds of Formula VI:

wherein R₁₁ and R₁₂ are either the same or different, may be takentogether, hydrogen, hydrocarbon C₁-C₂₀, saturated or unsaturated,aromatic or non-aromatic, cyclic or non-cyclic, hydroxyl, ether, amine,substituted amine, carboxylate, ester, amide, and may be substituted atleast once with a halide, hydroxyl, amine, amide, thiol, thioether,carboxylate, or a carbon structure of C₁-C₁₂ group which may besaturated or unsaturated and cyclic or non-cyclic, and which optionallymay be substituted with any of the above preceding groups, or mixturesthereof.

Additional compounds of Formula VI include those wherein R₁₁ and R₁₂ areeither the same or different, may be taken together, hydrocarbon C₁-C₁₂,saturated or unsaturated, cyclic or non-cyclic, hydroxyl, ether, amine,substituted amine, carboxylate, ester, amide, and may be substituted atleast once with a halide, hydroxyl, amine, amide, thiol, thioether,carboxylate, or a carbon structure of C₁-C₇ group which may be saturatedor unsaturated and cyclic or non-cyclic, and which optionally may besubstituted with any of the above preceding groups, includinghydrocarbon compounds acetaldehyde, butyraldehyde, glutaric dialdehyde,crotonaldehyde, benzaldehyde, acetone, methyl vinyl ketone,acetophenone, cyclohexanone, 2-cyclohexen-1-one, methyl acrylate, aceticanhydride, crotonic anhydride, phthalic anhydride, succinic anhydride,maleic anhydride, dimethyl adipate, diethyl phthalate, dimethylcarbonate, ethylene carbonate, diphenyl carbonate, phenyl carbamate,benzyl carbamate, methyl carbamate, urethane, propyl carbamate, ormixtures thereof.

Suitable ether compounds as reaction promoters include hydrocarboncompounds C₂-C₂₀, saturated or unsaturated, aromatic or non-aromatic,cyclic or non-cyclic, that have at least one C—O—C bond, and optionallyare substituted with at least one halide, hydroxyl, amine, thiol,thioether, carboxylic acid, ester, or a carbon structure of C₁-C₁₂ groupwhich may be saturated or unsaturated and cyclic or non-cyclic, andwhich optionally may be substituted with any of the above precedinggroups or mixtures thereof.

Additional ether compounds are hydrocarbon compounds of C₂-C₁₂ that haveat least one C—O—C bond, saturated or unsaturated, aromatic ornon-aromatic, cyclic or non-cyclic, and may be substituted at least oncewith a halide, hydroxyl, amine, ether, thiol, thioether, carboxylicacid, ester, or a carbon structure of C₁-C₇ group which may be saturatedor unsaturated and cyclic or non-cyclic, and which optionally may besubstituted with any of the above preceding groups including hydrocarboncompounds dimethyl ether, isopropyl ether, dipropyl ether, tert-amylmethyl ether, tert-butyl ethyl ether, allyl phenyl ether, allyl propylether, 4-methoxyphenyl ether, 3,3-dimethyl oxetane, dioxane,tetrahydropyran, tetrahydro-4H-pyran-4-ol, ethylene oxide, propyleneoxide, styrene oxide, glycidol, glycidyl methyl ether, glycidylbutyrate, glycidyl methacrylate, 1,2-epoxy-3-phenoxypropane,1,2-epoxyhexane, 1-chloro-2,3-epoxypropane, diethyl acetal,2,2-dimethoxypropane, 1,1-dimethoxycyclohexane, 2-hexenal diethylacetal, 3-chloropropionaldehyde diethyl acetal, benzaldehyde dimethylacetal, 1,1,3-trimethoxypropane, or a mixture thereof.

Alkene reaction promoters include hydrocarbon compounds C₂-C₂₀ thatinclude at least one C—C double bond or C—C triple bond, whether thecompounds are cyclic, heterocyclic or non-cyclic, and where thecompounds are optionally substituted at least once with a halide,hydroxyl, amine, ether, thiol, thioether, carboxylic acid, ester, or acarbon structure of C₁-C₁₂ group which may be saturated or unsaturatedand cyclic or non-cyclic, and which optionally may be substituted withany of the above preceding groups, or mixtures thereof.

Additional alkene reaction promoters include hydrocarbon compounds ofC₂-C₁₂ with at least one C—C double bond or C—C triple bond, cyclic,heterocyclic or non-cyclic, and may be substituted at least once with ahalide, hydroxyl, amine, ether, thiol, thioether, carboxylic acid,ester, or a carbon structure of C₁-C₇ group which may be saturated orunsaturated and cyclic or non-cyclic, and which optionally may besubstituted with any of the above preceding groups including hydrocarboncompounds 2-methylpropene, 1-butene, 2-butene, 2-methyl-2-butene,1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 2-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-2-pentenoic acid, 3-methyl-1-penten-3-ol, 5-chloro-1-pentene,4-bromo-2-methyl-2-butene, 1,4-pentadiene, 2,6-heptadienoic acid,hexatriene, cyclohexene, cyclohexadiene, cyclopentadiene,2-cyclopenten-1-one, 2-methylfuran, styrene, methylstyrene, methyl vinylketone, acrylic acid, methyl acrylate, 1-pentyne, 2-pentyne,2-pentyn-1-ol, 6-chloro-1-hexyne, 1,6-heptadiyne, or mixtures thereof.

Further reaction promoters include compounds of the formula RCOX, RSOX,RSO₂X, or RPOX wherein at least one carbon, sulfur, or phosphorus atomis double bonded with at least one oxygen atom or phosphorous halidessuch as PX₃ and PX₅ wherein X is at least one halide from the group F,Cl, Br, and I. R is at least one halide or hydrocarbon C₁-C₂₀ saturatedor unsaturated, cyclic or non-cyclic, and may be substituted at leastonce with a halide, hydroxyl, amine, ether, thiol or mixtures thereof.

Compounds where R includes chloro, bromo, methyl, ethyl, propyl,isopropyl, butyl, henyl, tolyl, naphthalyl, X includes F, Cl, Br, I,including compounds such as thionyl hloride, thionyl bromide, phosphorusoxybromide, phosphorus oxychloride, phosgene, acetyl chloride, acetylbromide, benzoyl chloride, benzoyl bromide, toluoyl chloride,toluenesulfonyl chloride, terephthaloyl chloride, terephthaloyl bromide,oxalyl dichloride, oxalyl dibromide, succinyl dichloride, glutaryldichloride, adipoyl dichloride, pimeloyl dichloride, methanesulfonylchloride, ethanesulfonyl chloride, propanesulfonyl chloride,isopropylsulfonyl chloride, butanesulfonylchloride, benzenesulfonylchloride, methyl dichlorophosphite, phosphoric acid halides, PCl₃, PBr₃,PCl₅, PBr₅, or mixtures thereof are suitable.

Compounds of the formula M_(a)X_(b) are also suitable reactionpromoters, wherein the bond dissociation energy of M-X is about lessthan 145 kcal/mol at 298° Kelvin and where M includes at least one metalor organic cation of the formula NR₄ ⁺, SR₃ ⁺, or PR₄ ⁺ where R includesC₁-C₆ which may be substituted at least one halide, hydroxyl, amine,ether, thiol or mixtures thereof and where X is at least one anion.

Inorganic or organic compounds defined above that are suitable are alsosoluble in water or organic solvents such as methanol, ethanol,isopropanol, methylene chloride, acetone, diethyl ether,tetrahydrofuran, ethylene glycol, xylene, and chlorobenzene. Thesecompounds include antimony halides, arsenic halides, barium halides,beryllium halides, bismuth halides, boron halides, cadmium halides,calcium halides, cerium halides, cesium halides, cesiumtetrachloroaluminates, cobalt halides, copper halides, gold halides,iron halides, lanthanum halides, lithium halides, lithiumtetrachloroaluminates, magnesium halides, manganese halides, mercuryhalides, nickel halides, osmium halides, phosphorus halides, potassiumhalides, potassium hydrogen fluorides, potassium tetrachloroaluminates,rhodium halides, samarium halides, selenium halides, silver halides,sodium halides, tin halides, lanthanum halides, sodium hydrogenfluorides, sodium tetrachloroaluminates, sodium/potassiumtetracloroaurates, sodium/potassium/lithium/zinc/coppertetrafluoroborates, thalium halides, titanium chloride-aluminumchlorides (x:y), titanium halides, yttrium halides, zinc halides,zirconium halides, ammonium halides, tetraalkyl quaternary ammoniumhalides, aralkyl trialkylquaternary ammonium halides, arayltrialkylammonium halides, alkyl N-alkylimidazolium halides, aralkylN-alkylimidazolium halides, alkyl N-aralkylimidazolium halides,N-alkylpyridinium halides, N-alkylisoquinolinium halides,N-alkylquinolinium halides, triphenylphosphonium halides, haloalkyltriphenylphosphonium halides, carboxyalkyl triphenylphosphonium halides,carbalkoxyalkyl triphenylphosphonium halides, cycloalkyltriphenylphosphonium halides, alkenyl triphenylphosphonium halides,aralkyltriphenylphosphonium halides, hydroxyaralkyl phosphonium halides,tetraphenylphosphonium halides, trialkylsulphonium halides, includingbut not limited to, inorganic compounds where M includes Li⁺, Na⁺, K⁺,Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ti⁴⁺, Co²⁺, Ni²⁺, Cu⁺, Cu²⁺, Sn²⁺, Sn⁴⁺, Pb²⁺,Pb⁴⁺, Ce³⁺, and Ce⁴⁺, organic compounds where M includes ⁺N(CH₃)₄,⁺N(CH₂CH₃)₄, ⁺N(CH₂CH₂CH₃)₄, ⁺N(CH₂CH₂CH₂CH₃)₄, ⁺NPh₄, ⁺P(CH₃)₄,⁺P(CH₂CH₃)₄, ^(+P(CH) ₂CH₂CH₃)₄, ⁺P(CH₂CH₂CH₂CH₃)₄, ⁺PPh₄, ⁺S(CH₃)₃,⁺S(CH₂CH₃)₃, ^(+S(CH) ₂CH₂CH₃)₃, +S(CH₂CH₂CH₂CH₃)₃, ⁺SPh₃, pyridinium,imidazolium, pyrrolidinium, and pyrrolium, and X includes inorganic Xincludes Cl⁻, Br⁻, I⁻, S²⁻, O²⁻, CO₃ ²⁻, SO₃ ²⁻, SO₄ ²⁻, NO₂ ⁻, NO₃ ⁻,BR₄ ⁻, OH⁻, PO₃ ²⁻, PO₄ ²⁻, ClO₄ ⁻, MnO₄ ⁻; organic X includes HCO₂ ⁻,CH₃CO₂ ⁻, CH₃ ⁻, CH₃CH₂ ⁻, pH⁻, CH₃O⁻, CH₃CH₂O⁻, PhO⁻, CH₃S⁻, CH₃CH₂S⁻,PhS⁻, CH₃NH⁻, CH₃CH₂NH⁻, PhNH⁻ or mixtures thereof.

The reaction promoter may also be water alone or as an aqueous solutionor aqueous suspension, that contains other components therein, such asone or more of the promoters mentioned above.

Optionally, a combination of at least one Lewis acid and at least onereaction promoter, i.e. a reaction facilitator, is prepared before beingadded to the reactants.

The term “solvent” includes hydrocarbon compounds C₁-C₂₄ saturated orunsaturated, cyclic or non-cyclic, aromatic or non-aromatic, optionallysubstituted with at least one halide, nitro, or sulfide group. Preferredsolvents are hydrocarbons C₁-C₈, saturated or unsaturated, such asnitroalkanes, heptane, cyclohexane, benzene, nitrobenzene,dinitrobenzene, toluene, xylene, 1,1,2,2-tetrachloroethane,dichloromethane, dichloroethane, ether, dioxane, tetrahydrofuran,benzonitriles, dimethylsulfoxide, tetramethylene sulfone, carbondisulfide, and benzene rings substituted with at least one halide suchas chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene,difluorobenzene, trifluorobenzene, bromobenzene, dibromobenzene,tribromobenzene, or mixtures thereof.

The products of the present process include halo-bisaryl-1,3,5-triazinecompounds or trisaryl-1,3,5-triazine compounds wherein the aromaticcompounds include a C₅-C₂₄ unsaturated ring, such as cyclopentadiene,phenyl, biphenyl, indene, naphthalene, tetralin, anthracene,phenanthrene, benzonaphthene, fluorene, which may be substituted in oneor more positions with a halide, an hydroxyl, an ether, a polyether, athiol, a thioether, an amine, such as —NHR, —NR₂, —NRR′, a carboxylicacid, an ester, an amide or a C₁-C₁₂ group which may be saturated orunsaturated and cyclic or non-cyclic, and which optionally may besubstituted with any of the above preceding groups. A general structureof useful compounds is shown above in Formulas I and III.

Preferred products include chloro-bisaryl-1,3,5-triazine compounds ortrisaryl-1,3,5-triazine compounds wherein the aromatic substituentsinclude phenyl, an ortho, meta, and/or para substituted phenyl ring, anaphthalene ring substituted at one or more positions, substituted orunsubstituted biphenyl, or tetralin ring substituted at one or morepositions, wherein the substitution group is a lower alkyl such asmethyl, ethyl, propyl, butyl, iso-butyl, t-butyl, pentyl, hexyl, septyl,octyl, nonyl, hydroxy, an ether group such as methoxy, ethoxy,propyloxy, octyloxy, nonoxy, or a halogen, such as fluoride, chloride,bromide, or iodide.

Other suitable products include chloro-bisaryl-1,3,5-triazine compounds,trisaryl-1,3,5-triazine compounds, or2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazine compounds wherein the aromaticsubstituted compounds include o-xylene, m-xylene, p-xylene, o-cresol,m-cresol, p-cresol, mesitylene, trimethylbenzene, cumene, anisole,ethoxybenzene, benzene, toloune, ethylbenzene, biphenyl,tert-butylbenzene, propoxybenzene, butoxybenzene, o-methoxyphenol,m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol,p-ethoxyphenol, o-nonoxyphenol, m-nonoxyphenol, tetralin,2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(4-alkoxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-chloro-4,6-bisphenyl-1,3,5-triazine;2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine;2-(4-alkoxy-2-hydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine;2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-hexyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;and2-(2-hydroxy-4-isooctyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

The term “step-wise” means a reaction sequence wherein a series ofreactions are conducted, the first reaction producing a compound ofFormula III and being carried out to about 50% to about 100% completionprior to addition of a compound of Formula IV to produce a compound ofFormula I. Preferably the reaction is carried out to about 70% to about100% completion prior to addition of compound of Formula IV, and morepreferably to about 75% to about 100% completion.

The term “continuous” means a reaction sequence not defined as“step-wise.”

The relative amounts of the reactants are as follows. The amount of acyanuric halide should be in sufficient amounts to react with aromaticcompounds of Formula II to produce either2-halo-4,6-bisaryl-1,3,5-triazine or 2,4,6-trisaryl-1,3,5-triazine. Theamount of aromatic compound of Formula II is important to ensure that asufficient amount of monohalo-bisaryl-triazine is synthesized withoutexcessive amounts of undesired side products such as2,4-dihalo-6-aryl-1,3,5-triazine or trisaryl triazine. Moreover, excessamounts of aromatic compounds can lead to undesired productdistributions enriched in mono- and tris-aryl triazines, thus, makingproduct separation and purification difficult and resource consuming.

The amount of aromatic compounds should be in sufficient amounts tosynthesize 2-halo-4,6-bisaryl-1,3,5-triazine,2,4,6-trisaryl-1,3,5-triazine, or convert2-halo-4,6-bisaryl-1,3,5-triazine into 2,4,6-trisaryl-1,3,5-triazine.Preferably, there should be between about 1 to about 5 mol equivalentsof aromatic compound of Formula II to cyanuric halide. More preferably,the amount of aromatic compound of Formula IV should be between about0.5 to about 2.5 mol equivalents of aromatic compound of Formula IV tocyanuric halide. In some cases aromatic compounds of Formula II can beused both as a reactant and a solvent.

The amount of Lewis acid used in the reaction facilitator should be insufficient amounts to transform 2,4,6-trihalo-1,3,5-triazine to thepreferred 2-halo-4,6-bisaryl-1,3,5-triazine or2,4,6-trisaryl-1,3,5-triazine. The amount of Lewis acid should bebetween about 0.5 to about 500 mol equivalents. Preferably, the amountof Lewis acid should be between about 1 to about 10 mol equivalents tocyanuric halide.

The amount of reaction promoter used in the reaction facilitator shouldbe in sufficient amounts to transform 2,4,6-trihalo-1,3,5-triazine, tothe preferred 2-halo-4,6-bisaryl-1,3,5-triazine or convert2-halo-4,6-bisaryl-1,3,5-triazine to the compound of Formula I.Preferably, the amount of reaction promoter should be between about 0.01to about 5 mol equivalents to cyanuric halide

The Lewis acid and reaction promoter preferably combine to form areaction facilitator complex that can be prepared in situ or preformedprior to addition to the reagents. The Lewis acid and/or reactionpromoter or reaction facilitator can be combined with either a compoundof Formula II or compound of Formula IV or both in any manner. In situreaction facilitator preparation comprises addition of at least oneLewis acid and at least one reaction promoter to a mixture of cyanurichalide, at least one aromatic compound of Formula II, and optionallysolvent without regard to addition order. To prepare the reactionfacilitator prior to addition to the reagents, i.e., the pre-formedmethod, Lewis acid and reaction promoter are combined and allowed to mixprior to addition, optionally in an inert solvent. Thereafter, thereaction facilitator is added to the reagents or vice versa, as desiredand in any addition order. As used herein, one or more Lewis acids maybe used, the first step and second step Lewis acid may be the same ordifferent. Additionally, one or more reaction promoters may be used, thefirst step and second step reaction promoter may be the same ordifferent. In the “continuous” process, the use of additional Lewis acidand reaction promoter is optional.

If the reaction facilitator is prepared using the pre-formed method,preferred mixing time of the Lewis acid and reaction promoter, prior toaddition to the reagents, is between about 1 minute to about 10 hours,more preferred is between about 10 minutes to about 5 hours. Thepreferred mixing temperature of the Lewis acid and reaction promotercombination, prior to addition to the reagents, is between about −50° C.to about 100° C., more preferred is between about −10° C. to about 50°C.

The reaction should run for sufficient time, at a sufficient temperatureand pressure to synthesize the desired triazine compound. The preferredreaction time for the synthesis of compounds of Formula III, i.e., thefirst step, is between about 5 minutes and about 48 hours, morepreferred between about 15 minutes and about 24 hours. The preferredreaction time for the synthesis of compounds of Formula I, i.e., thesecond step, is between about 10 minutes and about 24 hours, morepreferably between about 30 minutes and about 12 hours. The use of thereaction facilitator reduces the reaction time while improving theselectivity for mono-halo-bis-aryl products in the first step. Thepreferred reaction temperature for the first step is between about −50°C. and about 150° C., more preferred between about −30° C. and about 50°C. One advantage of using the reaction facilitator is the elimination ofthe need to heat the reaction mixture to increase the rate of reaction.Additionally, due to the use of the reaction facilitator, the reactiontemperature can be maintained at about ambient or lower temperatures,thus increasing product selectivity. The reaction pressure is notcritical and can be about 1 atm or higher if desired. An inert gas suchas nitrogen or argon is preferred. The preferred reaction temperaturefor the second step is between about 0° C. and about 120° C., morepreferred between about 20° C. and about 100° C.

The step-wise process comprises mixing cyanuric halide and the reactionfacilitator with one or more of the desired aromatic compounds,preferably until the reaction is about 70% to about 100% completed.Thereafter, the product of Formula III is isolated. The second aromaticcompound of Formula IV is added to the isolated product of Formula IIIalong with Lewis acid and optionally reaction promoter or reactionfacilitator to synthesize the trisaryl-triazine. The step-wise sequenceallows for the isolation, purification, and storage of Formula IIIproduct prior to subsequent reaction with compounds of Formula TV.

The continuous reaction comprises allowing a cyanuric halide to reactwith one or more aromatic compounds of Formula II in the presence of thereaction facilitator preferably until the reaction is about 70% to about100% complete. Thereafter, without isolating the product of Formula III,the second aromatic compound of Formula IV is allowed to react with theproduct of Formula III in the presence of optionally at least one secondLewis acid and optionally at least one second reaction promoter orreaction facilitator preferably until the reaction is about 70% to about100% complete. The continuous reaction eliminates the need to isolatethe intermediate product of Formula III or use of additional reagentssuch as solvents, and optionally Lewis acids, reaction promoters, orreaction facilitators. Moreover, the one-step process simplifies thesynthetic reaction pathway such that no unnecessary handling orprocessing of the reaction mixture is required until the reaction iscompleted.

To synthesize compounds of Formula III using the pre-formed reactionfacilitator method, the preferred addition time of the reactionfacilitator to a reagent mixture is between about 5 minutes to about 5hours, more preferred is between about 15 minutes to about 3 hours. Theaddition temperature of the reaction facilitator to a reagent mixture isbetween about −50° C. to about 150° C., preferred addition temperatureis between about −30° C. to about 50° C., and more preferred additiontemperature between about −20° C. to about 30° C.

To synthesize compounds of Formula I using the pre-formed reactionfacilitator, the preferred addition temperature of the reactionfacilitator to a reagent mixture is between about 0° C. to about 100°C., preferred addition temperature is between about 20° C. to about 80°C.

To synthesize compounds of Formula I, the preferred addition time of thecompound of Formula IV to the reaction mixture is between about 5minutes to about 10 hours, more preferred addition time is between about10 minutes to about 5 hours, and most preferred addition time is betweenabout 15 minutes to about 2 hours. The addition temperature of thecompound of Formula IV to the reaction mixture is between about 0° C. toabout 150° C., preferred addition temperature is between about 20° C. toabout 100° C.

The reaction facilitator should be present in amounts sufficient toreact with the number of halogens being substituted on the triazinecompound. A range of between about 1 to about 10 mol equivalents ofLewis acid and a range of between about 0.01 to about 5 mol equivalentsof reaction promoter can be used. The preferred Lewis acid is aluminumhalide, most preferably aluminum chloride. A preferred amount of Lewisacid is between about 2 to about 4 mol equivalents to halo-triazine. Apreferred amount of reaction promoter is between about 0.05 to about 2mol equivalents to triazine or triazine derived compounds.

The invention provides several advantages over prior art process such ashigher yields, greater selectivity of reaction products, higher reactionrates, and/or applicability of reaction conditions to various aromaticcompounds. The present invention consistently provided yields in therange of about 70 to about 98%, based on cyanuric halide conversion, asdetermined by HPLC analysis. Additionally, the ratio of desired2-halo-4,6-bisaryl-1,3,5-triazine to trisaryl-1,3,5-triazineconsistently averaged about 70:30 or more. The reaction facilitatorsignificantly increased reaction rates in comparison to state of the artwith Lewis acids alone. Moreover, the reaction conditions provided highyield and selectivity for a variety of aromatic compounds regardless ofthe aromatic substituents.

The triazine compounds synthesized using the present process can beapplied to a variety of applications such as those described in U.S.Pat. No. 5,543,518 to Stevenson et al. Col. 10-19, the content of which,as noted above, is expressly incorporated by reference herein.

The 2-chloro-4,6-bisaryl-1,3,5-triazines are not only importantintermediates for the preparation of trisaryl triazine TV absorbers, butthey are also valuable intermediates for a variety of other commerciallyimportant products, such as vat dyestuffs (GB 884,802), photographicmaterial (JP 09152701 A2), optical materials (JP 06065217 A2), andpolymers (US 706424; DE 2053414, DE 1246238). These compounds are alsoof interest for medicinal applications (e.g., see: R. L. N. Harris,Aust. J. Chem., 1981, 34, 623-634; G. S. Trivedi, A. J. Cowper, R. R.Astik, and K. A. Thaker, J. Inst. Chem., 1981, 53(3), 135-138 and141-144).

EXAMPLES

Certain embodiments and features of the invention are illustrated, andnot limited, by the following working examples.

The reaction progress can be monitored by HPLC or TLC. Further productcharacterization may be done by LCMS, MS, NMR, UV, direct comparisonwith authentic examples, or analytical techniques which are well knownin the art. A typical HPLC analysis of the samples is carried out asfollows. The reaction mixture may, in some cases be a two-phase system,with a lower, viscous liquid layer which may contain most of thereaction products (as AlCl₃ complexes), and a supernatant, which maycontain very little material. This supernatant can be often enriched inunreacted cyanuric chloride. In case of a two-phase system, it isimportant that both phases are sampled together in a representativefashion. For example, the mixture can be stirred rapidly and a sampletaken from the middle of the mixture using a polyethylene pipette withthe tip cut off. When pipetting the sample into a vial for work-up, itis important that the contents of the pipette be completely discharged.Since the two phases will separate into upper and lower layers, partialdischarge may result in a sample enriched in the lower layer.

The reaction sample is discharged into a 4-dram vial containing eitherchilled 5% HCl, or a mixture of 5% HCl and ice. The precipitate can beextracted with ethyl acetate and the water layer can be pipetted off.The ethyl acetate layer is then washed with water. Finally, anapproximately 10% solution of the ethyl acetate layer in acetonitrile isprepared for HPLC analysis.

Certain embodiments and features of the invention are illustrated, andnot limited, by the following working examples.

Example 1 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine without a ReactionPromoter

Cyanuric chloride (1.84 g) was allowed to react with 1.9 eq of m-xyleneand 2.5 eq (3.35 g) of AlCl₃ in 25 mL of chlorobenzene at 5° C. for 0.5h and then at room temperature for 3 h. Analysis by HPLC, after 2.5 h,showed that less than 8% of cyanuric chloride had reacted to form only2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine, no2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine were present. The reactionwas allowed to continue at room temperature. After 24 hours, HPLCanalysis showed about 51% cyanuric chloride conversion and formation of2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in the ratio of95:5, respectively. No 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine wasdetected.

Example 2 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine without a ReactionPromoter

Cyanuric chloride (1.84 g) was allowed to react with 2.05 eq of m-xyleneand 2.5 eq (3.35 g) of AlCl₃ in chlorobenzene at 5° C. for 2 h and thenat 15° C. for 5 h. Analysis by HPLC showed about 5% conversion ofcyanuric chloride to 2,4-bischloro-6-(2,4-dimethylphenyl)-1,3,5-triazineand no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine. The reaction was allowedto continue at room temperature. After 22 hours, HPLC analysis showedabout 55% cyanuric chloride conversion and formation of2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in the ratio of96:4, respectively. The reaction was allowed to continue. After 72 hoursat room temperature, a final HPLC analysis showed 99% cyanuric chlorideconversion, formation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in the ratio of 78:22, andno 2,4-bischloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.

Example 3 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.1 eqresorcinol and 2.5 eq AlCl₃

Cyanuric chloride was allowed to react with 2.05 eq of m-xylene inchlorobenzene, in the presence of 2.5 eq of AlCl₃ and 0.1 eq ofresorcinol. The reaction was carried out at about 5° C. for 2 h and thenat room temperature for 5 h. Analysis by HPLC showed about 10%conversion of cyanuric chloride to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine. After about 40 h atroom temperature, HPLC analysis showed 99% cyanuric chloride conversionto 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine present in a 78:22 ratiorespectively, no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine wasdetected.

Example 4 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eqresorcinol and 2.5 eq AlCl₃ and conversion to2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

Cyanuric chloride (1.84 g) was allowed to react with 1.9 eq of m-xylene,in the presence of 2.5 eq of AlCl₃ (3.35 g) and 0.2 eq of resorcinol, in25 mL chlorobenzene at about 5° C. for 0.5 h and then at roomtemperature for 3 h. Analysis by HPLC showed about 14% conversion ofcyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine.After about 13 h at room temperature, HPLC analysis showed 99% cyanuricchloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 82:18,respectively. No 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine orresorcinol-containing products were detected.

To the reaction mixture was added an additional 0.9 eq resorcinol andthe reaction mixture was heated at 80° C. for 1 h. HPLC analysisindicated the formation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 79:21 ratio, withabout 1% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.The process to make2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine wascomplete within 15 hours.

The heating was discontinued and the reaction mixture allowed to cool toroom temperature. 2% ice-cold aqueous HCl was added with stirring tobreak the aluminum complexes. A yellow precipitate was formed. Thereaction mixture was filtered, washed with water, and dried to give 3.65g of crude2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 5 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using1 eq resorcinol and 2.5 eq AlCl₃

Cyanuric chloride (1.84 g) was allowed to react with 2.05 eq ofm-xylene, in the presence of 2.5 eq of AlCl₃ (3.35 g) and 1 eq ofresorcinol, in 25 mL chlorobenzene at about 5° C. for 2 h and then at15° C. for 4 h. Analysis by HPLC showed 70% conversion of cyanuricchloride, mainly to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 59:41 ratio. Twominor components were also present,2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine (5%) and2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (3%).The reaction mixture was allowed to warm to room temperature, and afterabout 16 h at room temperature, HPLC analysis showed 92% cyanuricchloride conversion, mainly to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (66%),2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(25%), 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (4.5%), and2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and2-chloro-4-(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine(3%).

Example 6 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.5 eq resorcinol and 2.5 eq AlCl₃

Cyanuric chloride was allowed to react with 2 eq of m-xylene, in thepresence of 2.5 eq of AlCl₃ and 0.5 eq of resorcinol, in chlorobenzeneat room temperature for about 22 h. Analysis of the reaction mixture byHPLC showed about 94% cyanuric chloride conversion, mainly to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine,2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in aratio of 69:27:4.

Example 7 Synthesis of chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineusing 3 eq AlCl₃

A. Absence of a Reaction Promoter

Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in thepresence of 3 eq of AlCl₃, in chlorobenzene at 5° C. for 0.5 h and thenat room temperature for 3 h. An HPLC analysis showed about 3% cyanuricchloride conversion to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine; no2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected. After 24 hat room temperature, HPLC analysis showed about 33% conversion tocyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazineand 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a96:4 ratio respectively.

B. Effect of 0.2 eq of Resorcinol

Thereafter, 0.2 eq of resorcinol was added to the above reactionmixture, and the reaction mixture was further stirred at roomtemperature for 16 h. HPLC analysis showed 97% cyanuric chlorideconversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and^(2,4,6)-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in an 80:20ratio respectively; no2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.

Example 8 Synthesis of2-(214-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.2 eq resorcinol and 3 eq AlCl₃

Cyanuric chloride was allowed to react with 1.9 eq of m-xylene, in thepresence of 3 eq of AlCl₃ and 0.2 eq of resorcinol, in chlorobenzene at5° C. for 0.5 h and then at room temperature for 3 h. An HPLC analysisafter 3 h at room temperature showed about 20% cyanuric chlorideconversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. Thereaction mixture was stirred overnight at room temperature. After 18 h,an HPLC analysis showed 97% cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and^(2,4,6)-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in an 81:19ratio respectively; no2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.

To the reaction mixture was then added 0.9 eq of resorcinol, and themixture was heated in an oil bath to 60° C. (oil bath temperature).After 5 h, analysis by HPLC showed the formation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (73%)and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (21%), with 3% ofunreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 9 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.2 eq resorcinol and 2.75 eq AlCl₃

Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in thepresence of 2.75 eq of AlCl₃, and 0.2 eq of resorcinol in chlorobenzeneat 5° C. for 0.5 h and then allowed to warm to room temperature. After atotal of 18 h at room temperature, analysis by HPLC showed 98% cyanuricchloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in an 81:19 ratiorespectively; no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine wasdetected. The reaction mixture was then allowed to react with 0.9 eq ofresorcinol at 60° C. for 5 h. HPLC analysis showed the formation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 77:21 with1% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 10 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.2 eq resorcinol and 1.8 eq AlCl₃

Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in thepresence of 1.8 eq of AlCl₃, and 0.2 eq of resorcinol in chlorobenzeneat 5° C. for 0.5 h and then allowed to warm to room temperature. After18 h at room temperature, HPLC analysis showed 84% cyanuric chlorideconversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a 46:54 ratio.2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was the major product, andabout 3% 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was alsopresent.

The reaction was allowed to continue at room temperature. After 4 days,HPLC analysis showed 93% cyanuric chloride conversion, with thefollowing product distribution: 75%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine; 17%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 4%2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and otherresorcinol-containing components as minor products.

Example 11 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.144 eq resorcinol and 1.8 eq AlCl₃

Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in thepresence of 1.8 eq of AlCl₃ and 0.144 eq of resorcinol, in chlorobenzeneat 5° C. for 0.5 hand then at room temperature for 3 h. The ratio ofAlCl₃ to resorcinol was thus 12.5:1. An HPLC analysis after 65 hours atroom temperature showed 91% cyanuric chloride conversion, with thefollowing product distribution: 79%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine; 10%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 8%2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and otherresorcinol-containing compounds as minor products.

Example 12 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.15 eq resorcinol and 2.5 eq AlCl₃ in a tetrachloroethane solvent

Cyanuric chloride was allowed to react with 1.9 eq of m-xylene, in thepresence of 0.15 eq of resorcinol and 2.5 eq of AlCl₃, in1,1,2,2-tetrachloroethane at room temperature for about 26 h. HPLCanalysis showed about 95% cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in an 87:13 ratio.The reaction mixture was allowed to react with an additional 0.9 eq ofresorcinol for 4 h at 90° C. HPLC analysis showed 98.3%2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine conversion, and theratio of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 84:16.

Example 13 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.2 eq resorcinol and 3 eq AlCl₃ in a tetrachloroethane solvent

Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in thepresence of 3 eq of AlCl₃ and 0.2 of resorcinol, in chlorobenzene at 5°C. for 0.5 h and then at room temperature for 3 h. The first step(conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine) wascompleted in less than 16 h, with more than 98% cyanuric chlorideconversion as determined by HPLC analysis.2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine were formed in an 86:14ratio; no other products were detected. The reaction mixture was allowedto react with additional resorcinol at 110° C. for 1.5 h. HPLC analysisshowed a product mixture of 82%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 14%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2%2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, with only 1.5% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 14 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine usingmethyl alcohol with 3 eq AlCl₃

A two-neck round bottom flask was equipped with a reflux condenser, anargon inlet, a magnetic stirring bar and a glass stopper. Cyanuricchloride (3.7 g) and 50 mL of chlorobenzene were added. Next, 3 eq ofAlCl₃ (8 g) at ice-bath temperature was added, followed by 0.4 mL ofmethyl alcohol. After 5 min, 1.9 eq of m-xylene was added. The coolingwas removed, and the reaction mixture was stirred at room temperature.The reaction was complete within 20 h at room temperature, as indicatedby HPLC which showed the absence of m-xylene and 97% conversion ofcyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in an 83:17 ratio.

To the reaction mixture was added 1.1 eq of resorcinol, and the reactionmixture was heated at 85° C. for 4.5 h. HPLC analysis showed theformation of 78%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 19%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.6% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 1.4%2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine. The reaction wasallowed to cool to room temperature, and 2% ice-cold aqueous HCl wasadded. A yellow precipitate was formed, separated by filtration, washedwith water, and dried to yield 7.7 g of crude2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 15 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eqresorcinol and 2.5 eq AlCl₃ at 45° C.

Cyanuric chloride was allowed to react with 1.9 eq m-xylene, in thepresence of 2.5 eq AlCl₃ and 0.2 eq resorcinol, in chlorobenzene at 45°C. HPLC analysis of the reaction after 4 h showed 95% conversion ofcyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed ina 67:33 ratio respectively.

Example 16 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.2 eq resorcinol and 2.5 eq AlCl₃ in a dichlorobenzene solvent

Cyanuric chloride was allowed to react with 2 eq m-xylene, in thepresence of 2.5 eq AlCl₃ and 0.2 eq of resorcinol, inortho-dichlorobenzene at 24° C. After about 21 h, an exotherm wasobserved. A sample was immediately taken. HPLC analysis of the sampleshowed 94% conversion of cyanuric chloride to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in an 81:19 ratio. Afterthe exotherm had subsided, the cyanuric chloride conversion hadincreased to 97.5%, and the2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine ratio was 79:21.

To this mixture was added 0.9 eq additional resorcinol, and the mixturewas heated to 80° C. for 1 h. HPLC analysis of the reaction showed2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, witha 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(xylyl)-1,3,5-triazine ratio of 77:23, and about 2% unreactedbisaryl-chloro-triazine.

Example 17 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eqresorcinol and 2.5 eq AlCl₃ in a dichlorobenzene solvent

A. No Cooling During Exotherm

Cyanuric chloride was allowed to react with 2 eq m-xylene, in thepresence of 2.5 eq AlCl₃ and 0.2 eq of resorcinol, inortho-dichlorobenzene at 40° C. A 4° C. exotherm was observed after 4-5h. HPLC analysis of the reaction at this point showed 96% conversion ofcyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed ina 78:22 ratio.

B. With Cooling to 10° C. After 4 h

The reaction of part (A) was repeated. The exotherm began after 4 h. Asample was immediately taken, and the reaction was cooled to 10° C. HPLCanalysis of the sample showed 96% conversion of cyanuric chloride to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a78:22 ratio. There was also some unreacted2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine at this point. After1 h at 10° C., the cyanuric chloride conversion was 97%, no2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected, and theratio of 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 83:17.

Example 18 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.2 eq resorcinol and 3 eq AlCl₃ with 6.5% concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ and0.2 eq of resorcinol in chlorobenzene, was added 6.5% (based on theweight of cyanuric chloride) of concentrated HCl at ice-bathtemperature. An immediate reaction with AlCl₃ was observed, leading toits almost complete solvation of AlCl₃. 1.9 eq of m-xylene was thenadded. Within 5 min the color changed from light yellow to dark yellowto orange and finally dark red. The cooling bath was removed and thereaction mixture was analyzed at this stage by HPLC. The HPLC analysisshowed 99% cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a92:8 ratio. Thereafter, the reaction mixture was allowed to react with1.1 eq of resorcinol and subsequently, heated between 85°-90° C. for 1h. HPLC analysis of the reaction mixture showed 85.3%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,12.8% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 1.7% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 19 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using3 eq AlCl₃ with 6.5% concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ inchlorobenzene, was added 6.5% (based on the weight of cyanuric chloride)of concentrated HCl at ice-bath temperature. Within 1.5 h, the HPLCanalysis showed almost complete conversion of cyanuric chloride to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a ratio of91:9. Thereafter, the reaction mixture was allowed to react with 1.1 eqof resorcinol and subsequently heated at 85° C. for 1 h. HPLC analysisshowed the formation of 83.3%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,14.9% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 1.7% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. Notrisresorcinol-triazine or bisresorcinol-triazine products weredetected.

Example 20 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using3 eq AlCl₃ with 13% concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃, and1.9 eq of m-xylene in chlorobenzene, was added 13% (based on the weightof cyanuric chloride) of concentrated HCl at ice-bath temperature.Within 30 min at room temperature, 97% of the cyanuric chloride hadreacted, to produce 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 96:4; noside products were detected. Further stirring gave 99.5% cyanuricchloride conversion, with the ratio of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine unchanged and no otherproducts were detected. Thereafter, the reaction mixture was allowed toreact with 1.1 eq of resorcinol at 85° C. for 1.5 h. HPLC analysis ofthe reaction mixture showed the formation of 92.7%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 5%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2.3% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

The product was isolated by treating the reaction mixture with cold 2%aqueous HCl. Precipitate was collected by filtration, washed with water,and dried to give 92% yield of crude2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. Theactual yield should be even higher than 92%, since some of the productwas lost during the sampling for a number of HPLC analyses done duringthe course of the reaction. HPLC analysis of the isolated crude2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineshowed 92.4%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 5%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.35% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.25%2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.

Example 21 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl₃with 13% concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ inchlorobenzene, was added 13% (based on the weight of cyanuric chloride)of concentrated HCl at ice-bath temperature. After addition of 1.9 eq ofm-xylene and the reaction of cyanuric chloride with m-xylene wascomplete, as indicated by the absence of m-xylene by HPLC analysis, thereaction mixture was quenched with ice-cold 2% aqueous HCl at about 5°C. The reaction mixture was then extracted with methylene chloride. Theorganic layer was washed with water, dried over anhydrous sodiumsulfate, and the solvent removed under reduced pressure to give a whitesolid (quantitative yield based on m-xylene, and 95% yield based oncyanuric chloride). HPLC analysis indicated the isolated white solid toconsist of >96% pure2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 22 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 2.5 eq AlCl₃with 13% concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride, 2.5 eq of AlCl₃ inchlorobenzene, was added 13% (based on the weight of cyanuric chloride)of concentrated HCl at ice-bath temperature. HPLC analysis after 1 h atroom temperature showed 89% cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 82:18. Thereaction mixture was left stirring at room temperature overnight afterwhich the complete conversion of cyanuric chloride was detected. Thenext sample analyzed by HPLC after 22 h at room temperature showed 94%cyanuric chloride conversion, and the ratio of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine to be 43:57.

Example 23 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using2.5 eq AlCl₃ with 6.5% concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride, 2.5 eq of AlCl₃ inchlorobenzene, was added 6.5% (based on the weight of cyanuric chloride)of concentrated HCl at ice-bath temperature. After 22 h at roomtemperature, 98% of the cyanuric chloride had reacted to give2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in aratio of 90:10. The reaction mixture was allowed to react with 1.1 eq ofresorcinol and subsequently heated to 85° C. for 1.5 h. HPLC analysis ofthe reaction mixture showed 85.4%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,11.4% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.6% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.6%2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.

Example 24 Synthesis of 2-chloro-4,6-bistetralin-1,3,5-triazine

To a stirring mixture of 1 eq of cyanuric chloride (5 g., 0.027 mol) inchlorobenzene, maintained at ice bath temperature under nitrogen, wasadded 3 eq of AlCl₃ (10.87 g., 0.081 mol) over 5-10 min, followed by theaddition of conc. HCl (0.54 mL, 0.0065 mol) over 5-10 min, taking carethat the reaction temperature did not exceed 5° C. The reaction slurrywas stirred at 0-5° C. for another 10 min. The reaction was cooled to−10° C. and tetralin (7.01 mL, 0.0516 mol) was added at −10° C. over 2h. At the completion of the tetralin addition, the reaction mixture wasstirred at −10° C. for 2 h. The reaction was warmed to 0° C. and stirredfor 1 h. HPLC analysis of the reaction mixture showed 98.5% conversionof cyanuric chloride to 2-chloro-4,6-bistetralin-1,3,5-triazine and2,4,6-tristetralin-1,3,5-triazine in a 92:8 ratio. The slurry was warmedto 40° C. and resorcinol (3.29 g, 0.0298 mol) was added and the reactionmixture was stirred at 80° C. for 2 h. HPLC analysis showed 100%conversion of 2-chloro-4,6-bistetralin-1,3,5-triazine to2-(2,4-dihydroxyphenyl)-4,6-bistetralin-1,3,5-triazine.

Comparative Example 24 Synthesis of2-chloro-4,6-bistetralin-1,3,5-triazine

To a stirring mixture of 1 eq of cyanuric chloride (5 g., 0.027 mol) inchlorobenzene (50 mL), maintained at ice bath temperature undernitrogen, was added 3 eq of AlCl₃ (10.87 g., 0.081 mol) over 5-10 min.The reaction slurry was stirred at 0-5° C. for another 10 min. Thereaction was cooled to −10° C. and tetralin (7.01 mL, 0.0516 mol) wasadded at −10° C. over 2 h. At the completion of the tetralin addition,the reaction mixture was stirred at −10° C. for 2 h. The reaction waswarmed to 0° C. and stirred for 1 h. HPLC analysis of the reactionmixture showed no reaction of cyanuric chloride, and no formation of2-chloro-4,6-bistetralin-1,3,5-triazine.

Example 25 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl₃with concentrated sulfuric acid

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ inchlorobenzene, was added 0.24 eq of concentrated H₂SO₄ at ice-bathtemperature. After 5 min of stirring 2 eq of m-xylene was added. Afteranother 5 min, the cooling bath was removed and the reaction mixture wasstirred at room temperature. HPLC analysis after 2 h at room temperatureshowed 100% of the cyanuric chloride had reacted to give2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in aratio of 86:14.

Example 26 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using3.5 eq AlCl₃ with 10% aqueous sulfuric acid

To a stirring mixture of 1 eq of cyanuric chloride, 3.5 eq of AlCl₃ inchlorobenzene, was added 0.036 eq of sulfuric acid as a 10% aq. solutionat ice-bath temperature. After 10 min of stirring 1.9 eq of m-xylene wasadded. After 5 min at ice bath temperature the reaction mixture wasallowed to warm to 10° C. After 1 h 20 min. HPLC analysis showed 89% ofthe cyanuric chloride had reacted to give2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in aratio of 89:11. HPLC analysis, after 3 h at 9-11° C., showed 94% of thecyanuric chloride had reacted to give2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in aratio of 95:5. HPLC analysis, after 5 h at 9-11° C. and 17 h at roomtemperature, showed 98.5% of the cyanuric chloride had reacted to give2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in aratio of 97:3.

The reaction mixture was allowed to react with 1.1 eq of resorcinol andsubsequently heated to 85° C. for 3 h. HPLC analysis of the reactionmixture showed 92.7%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 4%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.4% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.9%2,4,6-(2,4-dihydroxyphenyl)-1,3,5-triazine.

Example 27 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl₃with benzoic acid

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ inchlorobenzene, was added 0.24 eq of benzoic acid as a 4% solution inchlorobenzene at ice-bath temperature. m-Xylene (1.95 eq) was thenadded. After 5 min at ice bath temperature, the reaction was allowed towarm to room temperature. HPLC analysis after 22 h at room temperature,showed 99.5% of the cyanuric chloride had reacted to give2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in aratio of 82:18.

Example 28 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using3 eq AlCl₃ and 6.5% concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ inchlorobenzene, was added 0.24 eq of concentrated HCl at ice-bathtemperature. After 45 min, 0.95 eq of m-xylene and 0.95 eq of toluenewere added. After 45 min at ice bath temperature, the reaction wasstirred at 9° C. for 1 h and then at room temperature for 2 h. HPLCanalysis showed 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine asthe major product with lesser mounts of2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine, and2-chloro-4-(4-methylphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine.

The reaction mixture was allowed to react with 1.1 eq of resorcinol andsubsequently heated to 85° C. for 2 h. HPLC analysis of the reactionmixture showed2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine asthe major product with lesser amounts of2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, and2-(2,4-dihydroxyphenyl)-4-(4-methylphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine.

Example 29 Synthesis of2-(2,4-dimethoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using3 eq AlCl₃ with concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ inchlorobenzene, was added 0.24 eq of concentrated HCl at ice-bathtemperature. After 10 min, 1.9 eq of m-xylene was added. The reactionwas stirred at ice bath temperature for 2 h and then at room temperaturefor 5 h. HPLC analysis showed formation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major productand 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 91:9 ratio. Thereaction mixture was allowed to react with 1.1 eq of1,3-dimethoxybenzene. The mixture was heated to 59-61° C. and stirredfor 2 h, then heated 85° C. and stirred for 5 h. HPLC analysis of thereaction mixture showed 76%2-(2,4-dimethoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and24% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (HPLC area percent at290 nm) as the only products.

Example 30 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 2.5 eq AlCl₃and 0.12 eq anhydrous HCl

To a mixture of cyanuric chloride in chlorobenzene cooled to 5° C. wasadded 2.5 eq of AlCl₃, 0.12 eq of anhydrous HCl (as a 0.28 N solution inchlorobenzene), and 1.9 eq of m-xylene. This mixture was warmed to 23°C. with stirring, and the progress of the reaction was monitored byHPLC. The data are given in Table I below.

TABLE I Reaction Profile for Anhydrous HCl Cyanuric Bis-xylyl- chlorideMono-xylyl-Bis- monochloro- Tris-xylyl- Time (h) Conversion (%)chloro-Triazine triazine Triazine 1 3 100 2 6 100 3 9 100 25 65 58 40 2The cyanuric chloride conversion is based on area percent at 210 nm. Theamounts of the other components are based on area percent at 290 nm.

Example 31 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl₃ and0.2 eq anhydrous HCl

To a mixture of cyanuric chloride in chlorobenzene cooled to 5° C. wasadded 3 eq of AlCl₃, 0.2 eq of anhydrous HCl (as a 0.156 N solution inchlorobenzene), and 1.9 eq of m-xylene. This mixture was then warmed to23° C. with stirring, and the progress of the reaction was monitored byHPLC. The data are given in Table II below.

TABLE II Reaction Profile for Anhydrous HCl (0.20 eq) Cyanuric ChlorideMonoxylyl- Bis-xylyl- Tris- Bisxylyl- Time Conversion bischloro-monochloro- xylyl- monochloro: (h) (%) triazine triazine triazineTris-xylyl* 1 2 100 2.5 6 100 4 15 97 3 5.5 19 97 3 23 59 89 10 1 94:6 48 88 0.5 65.5 34 78:22 *corrected ratio.

Example 32 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using0.2 eq resorcinol and 3 eq AlCl₃ with 0.55 eq H₂O

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ and0.2 eq of resorcinol in chlorobenzene, was added 0.55 eq of water atice-bath temperature. An immediate reaction with AlCl₃ was observed.After 10 min of stirring, 1.9 eq of m-xylene was added. After another 10min, the cooling bath was removed and the reaction mixture was stirredat room temperature. HPLC analysis of the reaction mixture after 1.5 hat room temperature showed 84% cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a 95:5 ratiorespectively. After 2.5 h at room temperature HPLC analysis showed 95%conversion of cyanuric chloride, and a ratio of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 94:6. Thereafter, 1 eqof resorcinol was added and the reaction mixture was stirred at 85° C.for 1 h. HPLC analysis of the reaction mixture showed 89.4%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 7.7%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.6% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 1.3%2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.

Example 33 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using3 eq AlCl₃ with 0.55 eq water

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ inchlorobenzene, was added 0.55 eq of water at ice-bath temperature. After10 min 1.9 eq of m-xylene was added. HPLC analysis after 30 min at roomtemperature showed 93% cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 94:6respectively. After 1 h at room temperature HPLC analysis showed 98%cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 92:8. After4.5 h at room temperature, HPLC analysis showed conversion of cyanuricchloride had increased to 99%, and the ratio of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 93:7.

Thereafter, 1.1 eq of resorcinol was added and the mixture stirred at85° C. for 2 h. HPLC analysis of the reaction mixture showed 91.1%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 6.3%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.8% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.75%2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.

Example 34 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 2.5 eq AlCl₃with 0.55 eq water

To a stirring mixture of 1 eq of cyanuric chloride, 2.5 eq of AlCl₃ inchlorobenzene, was added 0.55 eq of water at ice-bath temperature.Analysis by HPLC, after 30 min at room temperature, showed 92%conversion of cyanuric chloride to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 94:6. After1 h at room temperature, HPLC analysis of the reaction mixture showed96% conversion of cyanuric chloride, and a ratio of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 88:12. After 4.5 h atroom temperature, HPLC analysis showed 97% conversion of cyanuricchloride and a ratio of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 77:23.

Example 35 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3.25 eq AlCl₃with 0.55 eq water

To a stirring mixture of 1 eq of cyanuric chloride, 3.25 eq of AlCl₃ inchlorobenzene, was added 0.55 eq of water at ice-bath temperature. After10 min 1.9 eq of m-xylene was added. Within 1 h, 98% conversion ofcyanuric chloride was detected, based on HPLC analysis. The ratio of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 92:8. A final sampleanalysis after complete disappearance of m-xylene showed 99% cyanuricchloride conversion, and the ratio of the products,2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, was 89:11.

Example 36 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl₃without promoter

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl₃ inchlorobenzene was added. After 10 min 1.9 eq of m-xylene was added. HPLCanalysis after 2 h showed 5% cyanuric chloride conversion to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine. After 24 h at roomtemperature HPLC analysis showed 46% cyanuric chloride conversion to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in a 96:4.

Example 37 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3.25 eq AlCl₃without promoter

The cyanuric chloride was allowed to react with 2 eq of m-xylene in thepresence of 3.25 eq of AlCl₃ in chlorobenzene at 5° C. for 0.5 h andthen at room temperature for 3 h. HPLC analysis. After 4 h, showed about15% cyanuric chloride conversion to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine; no2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected. After 24 hat room temperature, HPLC analysis showed about 51% conversion ofcyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazineand 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a91:9 ratio.

Example 38 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3.5 eq AlCl₃without promoter

The cyanuric chloride was allowed to react with 2 eq of m-xylene in thepresence of 3.5 eq of AlCl₃ in chlorobenzene at 5° C. for 0.5 h and thenat room temperature for 3 h HPLC analysis. After 4 h, showed about 6%cyanuric chloride conversion to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine; no2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected. After 24 hat room temperature, HPLC analysis showed about 38% conversion ofcyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazineand 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a96:4 ratio.

Example 39 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine withdichloromethane and 2.5 eq AlCl₃

To a stirring mixture of 1 eq of cyanuric chloride 0.4 eq ofdichloromethane in chlorobenzene was added 2.5 eq of aluminum chlorideat ice-bath temperature, the cooling bath was removed and the reactionmixture stirred at room temperature. The HPLC analysis after 3 h at roomtemperature showed 14% of cyanuric chloride conversion to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine formed in a ratio of93:7. After about 14 h at room temperature, HPLC analysis showed 98.5%cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 87:13.

To the above reaction mixture, 1 eq of resorcinol was added and themixture stirred at 80-85° C. for 1 h. HPLC analysis of the reactionmixture showed 76% of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and14% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine.

Example 40 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine withdichloromethane, resorcinol and 2.5 eq aluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride, 0.4 eq ofdichloromethane, and 0.2 eq of resorcinol in chlorobenzene, was added2.5 eq of aluminum chloride at ice-bath temperature, the cooling bathwas removed and the reaction mixture stirred at room temperature. After15 min, 1.9 eq of m-xylene was added and after 15 min of stirring atice-bath temperature, the cooling bath was removed and the reactionmixture stirred at room temperature. HPLC analysis after 3 h at roomtemperature showed 95% of cyanuric chloride conversion to 2-chloro-4,6bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine formed in a ratio of 92:8.

To the above reaction mixture, 1 eq of resorcinol was added and themixture stirred at 80-85° C. for 1.5 h. HPLC analysis of the reactionmixture showed 80.5% of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and9.9% of 2,4,6-tris(2,4-dimethylphenyl) 1,3,5-triazine.

Example 41 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with2.3 eq of tert-butyl chloride and 2.5 eq aluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride and 2.5 eq ofaluminum chloride in chlorobenzene at ice bath temperature was added 2.3eq of tert-butyl chloride over 1 h. After 5 min. of stirring, 1.95 eq ofm-xylene was added over 5 min. The ice bath was replaced with a waterbath, and the reaction mixture was allowed to warmed to roomtemperature. After 5 min. at room temperature, HPLC analysis showed 97%of cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)1,3,5-triazine, present in a ratio of98:2,

To the above reaction mixture was added 1.1 eq of resorcinol, and themixture stirred at 80° C. for 3 h. HPLC analysis of the reaction mixtureshowed 94% of 2-(2,4-dihydroxyphenyl)-4,6bis(2,4-dimethylphenyl)-1,3-triazine, 3.5% of2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.5% of unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 42 Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 0.46 eq oftert-butyl chloride with 2.5 eq aluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride and 2.5 eq ofaluminum chloride in chlorobenzene at ice bath temperature was added0.46 eq of tert-butyl chloride over 10 min. After 5 min. of stirring,1.95 eq of m-xylene was added over 5 min. After 5 min., the ice bath wasreplaced with a water bath, and the reaction mixture warmed to roomtemperature. After stirring at room temperature for 22 h, HPLC analysisshowed 98% of cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of 84:16.

Example 43 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with0.5 eq tert-butylchloride. 0.2 resorcinol and 2.5 eq aluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride, 0.2 eq ofresorcinol, and 2.5 eq of aluminum chloride in chlorobenzene at ice bathtemperature was added 0.5 eq of tert-butyl chloride over 10 min. After 5min. of stirring, 1.95 eq of m-xylene was added. The ice bath wasreplaced with a water bath, and the reaction mixture was allowed to warmto room temperature. After stirring at room temperature for 2 h, HPLCanalysis showed 97% of cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of91:9.

To the above reaction mixture was added 1 eq of resorcinol, and themixture stirred at 78-82° C. for 3 h. HPLC analysis of the reactionmixture showed 86% of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 12%of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2% of unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 44 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine usingsodium hydroxide and 3 eq of aluminum chloride

To a stirring mixture of 3.7 g (1 eq) of cyanuric chloride, 8 g (3 eq)of aluminum chloride in 50 mL chlorobenzene, was added 0.4 mL of aqueoussodium hydroxide solution (50%) at ice-bath temperature. After 10 min ofstirring, 1.9 eq of m-xylene was added. The cooling bath was removed andthe reaction mixture stirred at room temperature. HPLC analysis after 30min at room temperature showed 91% of cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of96:4. A second sample analyzed after 1 h at room temperature showed 94%of cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 92:8. Aftera total of 4 h at room temperature, HPLC analysis showed 95% conversionof cyanuric chloride and a ratio of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 89:11.

To the above reaction mixture, 1.1 eq of resorcinol was added and themixture heated with stirring at 80° C. for 2 h. HPLC analysis of thereaction mixture showed 80% of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 16%of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.5% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2.2% of2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine.

Example 45 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine usingaluminum hydroxide with 3 eq aluminum chloride

To a stirring mixture of 3.7 g (1 eq) of cyanuric chloride, 8 g (3 eq)of aluminum chloride in 50 mL chlorobenzene was added 0.39 g (0.5 eq) ofaluminum hydroxide at ice-bath temperature. After 10 min of stirring,1.9 eq of m-xylene was added. The cooling bath was removed after 10 minand the reaction mixture stirred at room temperature. HPLC analysisafter 20 h at room temperature showed 98% of cyanuric chlorideconversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of80:20.

To the above reaction mixture, 1.1 eq of resorcinol was added and themixture heated with stirring at 80° C. for 2 h. HPLC analysis of thereaction mixture showed 74% of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 22%of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.5% of unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 1.4% of2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine.

Example 46 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine usingaq. ammonium hydroxide with 3 eq aluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in chlorobenzene at ice bath temperature was added 0.38 eq ofaq. ammonium hydroxide over 15 min. After 15 min. of stirring, 1.95 eqof m-xylene was added. The ice bath was replaced with a water bath, andthe reaction mixture was allowed to warm to room temperature. After 4 hat room temperature, HPLC analysis showed 97% of cyanuric chlorideconversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of89:11. After an additional 1 h at room temperature, the cyanuricchloride conversion was >99%% and the2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine ratio was at 89:11.

To the above reaction mixture was added 1.1 eq of resorcinol, and themixture stirred at 78-82° C. for 3 h. HPLC analysis of the reactionmixture showed 84% of2-(2,4-dihydroxylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 12%of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2% of unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 47 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine usingsodium methoxide and 3 eq aluminum chloride

To a stirring mixture of 3 eq of aluminum chloride in chlorobenzene atice bath temperature was added 0.5 eq of sodium methoxide over 15 min.The reaction mixture was warmed to room temperature for 0.5 h and thencooled back to ice bath temperature. To the reaction mixture was added 1eq of cyanuric chloride and 1.95 eq of m-xylene. The ice bach wasreplaced with a water bath, and the reaction mixture warmed to roomtemperature. After 7.5 h at room temperature, HPLC analysis showed 98%cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of75:25.

To the above reaction mixture was added 1.1 eq of resorcinol, and themixture stirred at 85° C. for 4 h. HPLC analysis of the reaction mixtureshowed 80% of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 18%of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine and 2% of unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 48 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine usingα-methylstyrene with 3 eq aluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of aluminumchloride in chlorobenzene was added 0.5 eq of α-methylstyrene atice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene wasadded. After another 10 min, the cooling bath was removed and thereaction mixture was stirred at room temperature. HPLC analysis after 16h at room temperature showed 96% of cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (tris-xylyl triazine),formed in a ratio of 73:27.

Example 49 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 3 eq aluminumchloride without promoter

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of aluminumchloride in chlorobenzene was added at ice-bath temperature. Afteraddition of m-xylene, the reaction mixture was allowed to stir at roomtemperature for a total of 24 h. HPLC analysis of the reaction mixtureshowed about 46% cyanuric chloride conversion to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratioof 96:4.

Example 50 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with butyrylchloride and 3 eq aluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of aluminumchloride in chlorobenzene was added 0.5 eq of butyryl chloride atice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene wasadded. After another 10 min, the cooling bath was removed and thereaction mixture was stirred at room temperature. HPLC analysis after 16h at room temperature showed 92% of cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of78:22.

Example 51 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine usingpyridine hydrochloride with 3.5 eq of aluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride and 3.5 eq ofaluminum chloride in chlorobenzene was added 0.5 eq of pyridinehydrochloride at ice-bath temperature. After 10 min of stirring, 1.9 eqof m-xylene was added. The reaction mixture was stirred for 1 h at icebath temperature, 3.5 h at 10° C., and 6.5 h at 15-20° C. HPLC analysisshowed 98% of cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of88:12.

To the above reaction mixture was added 1.1 eq of resorcinol, and themixture stirred at 85° C. for 3 h. HPLC analysis of the reaction mixtureshowed 86% of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 13%of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 1% of unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 52 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3.5 eqaluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride and 3.5 eq ofaluminum chloride in chlorobenzene, after 10 min of stirring, 1.9 eq ofm-xylene was added. HPLC analysis after 4 h at room temperature showed6% cyanuric chloride conversion to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine with no formation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The reactionmixture was stirred at room temperature for 24 h. HPLC analysis showedabout 38% conversion of cyanuric chloride to2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, in a 96:4 ratio.

Example 53 Synthesis of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine usingbenzyltriethylammonium chloride and resorcinol and 2.5 eq aluminumchloride

To a stirring mixture of 1 eq of cyanuric chloride, 0.2 eqbenzyltriethylammonium chloride, and 0.2 eq of resorcinol inchlorobenzene was added 2.5 eq of aluminum chloride at ice-bathtemperature. After 10 min. of stirring, 1.9 eq of m-xylene was added.The reaction mixture was stirred for 1 hour at ice bath temperature, and3 h at 18-20° C. HPLC analysis showed 72% of cyanuric chlorideconversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 86:14.

Example 54 Synthesis of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine usinglithium chloride with 3 eq of aluminum chloride

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in chlorobenzene was added 0.5 eq of lithium chloride atice-bath temperature. After 10 min. of stirring, 1.9 eq of m-xylene wasadded. The reaction mixture was allowed to stir at room temperature.HPLC analysis of the reaction mixture after 44 h of stirring at roomtemperature showed 97% cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 81:19.

To the above reaction mixture, 1.1 eq of resorcinol was added and themixture stirred at 70° C. for 3 hours. HPLC analysis of the reactionmixture showed 76% of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 20%of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1% of unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2% of2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine.

Example 55 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

Part A: Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.50 eq ofallyl bromide as promoter

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in chlorobenzene at ice bath temperature was added 0.5 eq ofallyl bromide over 20 min. An immediate reaction with aluminum chloridewas observed during the addition. After 10 min at 0-1° C., 1.9 eq ofm-xylene was added over 5 min. After 30 min at 0-1° C., the ice bath wasreplaced with a cold-water bath, and the reaction mixture was stirred at17-19° C. for 25.5 h. HPLC analysis showed 95% of cyanuric chlorideconversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ration of86:14. A small amount of by-product was detected, probably arising fromthe reaction of 2-chloro-4,6-(2,4-dimethylphenyl)-1,3,5-triazine (CDMPT)with allyl bromide, was observed. If this product is counted along withCDMPT itself, the bis-xylyl-mono-chloro-triazine to tris-xylyl-triazineratio increases to 89:11.

Part B: Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

To the above reaction mixture was added 1:1 eq resorcinol and themixture was stirred at 85° C. for 17 h. HPLC analysis of the reactionmixture showed 87%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and13% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine.

Example 56 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

Part A: Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine: using 0.4 eq of3-methyl-2-buten-1-ol as promoter

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in chlorobenzene at −13° C. to −15° C. was added 0.4 eq of3-methyl-2-buten-1-ol over 15 An immediate reaction with aluminumchloride was observed during the addition. The mixture was allowed towarm to 0-1° C. and after stirring for 10 min, 1.9 eq of m-xylene wasadded over 10 min. After stirring for 2 h at 0-1° C., the ice bath wasreplaced with a cold-water bath and the reaction mixture was stirred at15-16° C. for 18 h. HPLC analysis showed 94% of cyanuric chlorideconversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 86:14.

Part B: Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

To the above reaction mixture was added 1.1 eq of resorcinol and themixture was stirred at 85° C. for 2 h. HPLC analysis of the reactionmixture showed 84% of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 14%2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2% unreacted2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 57 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

Part A: Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.5 eq ofbenzoyl chloride as promoter

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in chlorobenzene at 1-2° C. was added 0.5 eq of benzoylchloride over 10 min. After stirring for 10 min, 1.9 eq of m-xylene wasadded over 6 min. After stirring for 2 h at 0-1° C., the ice bath wasreplaced with a cold water bath and the reaction mixture was allowed towarm to 15-16° C. and stirred for 19 h. HPLC analysis showed 84% ofcyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 86:14.

Part B: Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

To the above reaction mixture was added 1.1 eq of resorcinol and themixture was stirred at 85° C. for 2 h. HPLC analysis of the reactionmixture showed 80%2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and20% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine.

Example 58 Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.5 eq ofpropanesulfonyl chloride as promoter

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in chlorobenzene at 0-1° C. was added 0.5 eq of propanesulfonylchloride over 10 min. An immediate reaction with aluminum chloride wasobserved during the addition. After stirring for 10 min at 1-2° C., 1.9eq of m-xylene was added over 6 min. After stirring for 2 h at 0-2° C.,the ice bath was replaced with a cold water bath, the reaction wasallowed to warm to 16-18° C. and was stirred for 20 h. HPLC analysisshowed 92% of cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 90:10.

Example 59 Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.5 eq ofp-toluenesulfonyl chloride as promoter

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in chlorobenzene at 0-2° C. was added 0.5 eq ofp-toluenensulfonyl chloride over 10 min. After stirring for 10 min, 1.9eq of m-xylene was added over 6 min. After stirring at 0-1° C., the icebath was replaced with a cold water bath, the reaction mixture wasallowed to warm to 16-17° C. and was stirred for 21 h. The water bathwas removed and the temperature was allowed to warm to 23° C. HPLCanalysis showed the conversion of cyanuric chloride to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 79:21.

Example 60 Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.5 eq ofacetic anhydride as promoter

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in chlorobenzene at 1-2° C. was added a solution of 0.5 eq ofacetic anhydride in chlorobenzene over 10 min. An immediate reactionwith aluminum chloride (exotherm) was observed during addition. Afterstirring for 10 min, 1.9 eq of m-xylene was added over 6 min. Afterstirring at 0-1° C. for 2 h, the ice bath was replaced with a cold waterbath, the reaction mixture was allowed to warm to 16° C. and was stirredfor 19 h. HPLC analysis showed the complete conversion of m-xylene, butonly 72% conversion of cyanuric chloride to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 84:16.

Example 61 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine

Part A: Preparation of 2-chloro-4,6-bisphenyl-1,3,5-triazine usingconcentrated HCl as a Reaction Promoter

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was addedconcentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes,1.95 eq of benzene was added and the reaction mixture stirred at icebath temperature for 10 minutes. The cooling bath was removed, thereaction was allowed to warm to room temperature, and stirred. After 26h at room temperature, an HPLC analysis indicated about 86% cyanuricchloride conversion to 2-chloro-2,6-bisphenyl-1,3,5-triazine. Thestirring was continued for 24 h at room temperature. The HPLC analysisshowed the cyanuric chloride conversion to 92% with >96% being2-chloro-4,6-bisphenyl-1,3,5-triazine and less than 2% of2,4,6-trisphenyl-1,3,5-triazine. The result was confirmed by LCMS.

Part B: Preparation of2-(2,4-dihyrdroxyphenyl)-4,6-bisphenyl-1,3,5-triazine

To the above reaction mixture was added 1.1 eq of resorcinol and themixture was heated to 80° C. Within 2 h, HPLC analysis indicated about80% of 2-chloro-4,6-bisphenyl-1,3,5-triazine conversion to2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine.

Comparative Example 61 Preparation of2-chloro-4,6-bisphenyl-1,3,5-triazine without concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was added 1.95 eqof benzene and the reaction mixture was stirred at ice bath temperaturefor 10 minutes. The cooling bath was removed, the reaction mixture wasallowed to warm to room temperature, and stirred. After about 26 h, anHPLC analysis indicated almost no cyanuric chloride conversion and nopresence of 2-chloro-4,6-bisphenyl-1,3,5-triazine. The stirring wascontinued for an additional 24 h at room temperature. An HPLC analysisshowed almost no cyanuric chloride conversion and no2-chloro-4,6-bisphenyl-1,3,5-triazine.

Example 62 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine

Part A: Preparation of 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazineusing concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was addedconcentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes,1.9 eq of toluene was added and the reaction mixture was stirred at icebath temperature for 30 minutes. The cooling bath was removed, thereaction mixture was allowed to warm to room temperature, and stirredfor 21 h. HPLC analysis indicated about 95% cyanuric chloride conversionto 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine and the isomer2-chloro-4-(4-methylphenyl)-6-(2-methylphenyl)-1,3,5-triazine.

Part B: Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine

To the above reaction mixture was added 1.1 eq of resorcinol and themixture was heated to 80° C. Within 3 h, an HPLC analysis indicated2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine had converted to2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine. HPLCanalysis of the crude product showed 78% of2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 11% ofthe isomer with probable structure of2-(2,4-dihydroxyphenyl)-4-(4-methylphenyl)-6-(2-methylphenyl)-1,3,5-triazine.

Comparative Example 62 Preparation of2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine without concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was added 1.9 eqof toluene and the reaction mixture was stirred at ice bath temperaturefor 10 minutes. The cooling bath was removed, the reaction mixture wasallowed to warm to room temperature. After about 2 h, an HPLC analysisindicated no reaction of cyanuric chloride. The stirring was continuedfor about 20 h at room temperature. HPLC analysis showed almost noreaction of cyanuric chloride and the absence of2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine.

Example 63 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine

Part A: Preparation of2-chloro-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine using concentratedHCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was addedconcentrated HCl (13 wt % based on cyanuric chloride). After 30 minutes,the reaction was further cooled to about −5° C. and 1.9 eq of xylene wasadded. The reaction mixture was stirred at about 0° C. for 2 h, and thenat room temperature for 4 h. HPLC analysis indicated >95% cyanuricchloride conversion to 82%2-chloro-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine and 6% of itsisomer.

Part B: Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine

To the above reaction mixture was added 1.1 eq of resorcinol and themixture was heated to 80° C. Within 2 h, an HPLC analysis indicated2-chloro-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine and its isomer hadcompletely reacted to form 83% of2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine and6% of its isomer.

Comparative Example 63 Preparation of2-chloro-4,6-bis(3,4-methylphenyl)-1,3,5-triazine without concentratedHCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was added 1.9 eqof o-xylene and the reaction mixture was stirred at ice bath temperaturefor 1 h. The cooling bath was removed and the reaction mixture wasallowed to warm to room temperature. After about 2 h, an HPLC analysisindicated no reaction of cyanuric chloride. The stirring was continuedfor about 20 h at room temperature. HPLC analysis showed no significantconversion of cyanuric chloride and the absence of2-chloro-4,6-bis(3,4-methylphenyl)-1,3,5-triazine.

Example 64 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine

Part A: Preparation of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine usingconcentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was addedconcentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes,2 eq of biphenyl was added and the reaction was stirred at ice bathtemperature for 1 h. HPLC analysis indicated 88% cyanuric chlorideconversion to 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine as the majorproduct. The cooling bath was removed, the reaction mixture was allowedto warm to room temperature, and stirred. HPLC analysis after 3 h atroom temperature indicated about 93% cyanuric chloride to2-chloro-4,6-bis(4-biphenyl) as the major product and confirmed by MS.

Part B: Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine

To the above reaction mixture was added 1.1 eq of resorcinol and themixture was heated to 85° C. for 2 h. HPLC and MS analysis indicated theformation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine.

Comparative Example 64 Preparation of2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine without concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was added 2 eq ofbiphenyl and the reaction mixture was stirred at ice bath temperaturefor 1 h. HPLC analysis indicated almost no cyanuric chloride conversionand the absence of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine. Thecooling bath was removed and the reaction mixture was allowed to warm toroom temperature. After about 3 h, an HPLC analysis indicated noreaction of cyanuric chloride and no formation of2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine.

Example 65 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine

Part A: Preparation of2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine using concentratedHCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was addedconcentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes,1.95 eq of tert-butylbenzene was added and the reaction was stirred atice bath temperature for 10 minutes. The cooling bath was removed, thereaction mixture was allowed to warm to room temperature, and stirred.After 2 h, HPLC analysis indicated 62% cyanuric chloride conversion to2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine as the major product(>78%). The reaction mixture was stirred at room temperature for anadditional 24 h. HPLC analysis showed 83% cyanuric chloride conversionto 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine as the majorproduct (>72%), with the isomer.

Part B: Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine

To the above reaction mixture was added 1.1 eq of resorcinol and themixture was heated to 80° C. for 2 h. HPLC analysis indicated 63%formation of2-(2,4-dihyroxyphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine.

Comparative Example 65 Preparation of2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine without concentratedHCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene at ice bath temperature was added 1.95 eqof tert-butylbenzene. The reaction mixture was stirred at ice bathtemperature for 10 minutes. The cooling bath was removed, the reactionmixture was allowed to warm to room temperature, and stirred. Afterabout 2 h, an HPLC analysis indicated no reaction of cyanuric chlorideand no 2-chloro-4,6-(4-tert-butylphenyl)-1,3,5-triazine formation. Thestirring was continued for about 24 h at room temperature. HPLC analysisshowed no 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine formation.

Example 66 Preparation of2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine

Part A: Preparation of2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine using concentratedHCl

2-Chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine was preparedessentially following the procedure described in example 67.

Part B: Preparation of2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-tert-butylphenyl)-13,5-triazine

To the above reaction mixture was added 1.1 eq of 4-hexylresorcinol andthe mixture was heated to 80° C. for 3 h. HPLC analysis indicatedconversion of 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine to2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazineas the major product.

Example 67 Preparation of2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

Part A: Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

2-Chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine was prepared byallowing to react 1 eq of cyanuric chloride with 1.9 eq of m-xylene inthe presence of 3 eq of aluminum chloride and concentrated HCl inchlorobenzene as discussed above.

Part B: Preparation of2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

To the above reaction mixture was added 1.1 eq of resorcinol monooctylether and the mixture was stirred at room temperature for about 20 h.TLC analysis indicated formation of2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineas the major product by a direct comparison with a commercial sample of2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 68 Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

Part A: Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; Simultaneousaddition of cyanuric chloride and m-xylene to reaction facilitatorprepared from aluminum chloride and concentrated HCl

To a stirring mixture of 3 eq of aluminum chloride in chlorobenzene at0° C. to 5° C. was added concentrated HCl (6 wt % based on aluminumchloride), and the reaction mixture was stirred for 10 minutes to formthe reaction facilitator. To the mixture was added a solution of 1 eq ofcyanuric chloride and 1.9 eq of m-xylene in chlorobenzene at 0° C. to 5°C. and the reaction was stirred for 10 minutes. HPLC analysis indicated95% cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (99%). The reactionmixture was allowed to stir at 0° C. to 5° C. for 2 h. HPLC analysisshowed 99% cyanuric chloride conversion to2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (98%).

Part B: Preparation of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

To the above reaction mixture was added 1.1 eq of resorcinol and themixture was heated to 80° C. for 2 h. HPLC analysis indicated 95% of2-(2,4-dihyroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 69 Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in benzene assolvent and concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in benzene at 7° C. was added concentrated HCl (13% wt based oncyanuric chloride), and the mixture was stirred for 10 minutes. To thereaction mixture was added 1.9 eq of m-xylene and the reaction mixturewas stirred at 0° C. for 30-35 minutes. The cooling bath was removed,the reaction mixture was allowed to warm to room temperature, andstirred for 3 h. HPLC analysis indicated >97% cyanuric chlorideconversion to 2-chloro-4,6-(2,4-dimethylphenyl)-1,3,5-triazine (85%).

Example 70 Preparation of2-(2,4-dihydroxy-6-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

Part A: Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine complex withreaction facilitator prepared from aluminum chloride and concentratedHCl

To a stirring mixture of 1 eq of isolated2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 3 eq of aluminumchloride in o-dichlorobenzene was added concentrated HCl (5.9 wt % basedon aluminum chloride). After stirring for about 5-6 h at roomtemperature, the reaction turned orange-red, indicative of a new complexformed between the reaction facilitator, consisting of aluminum chlorideand concentrated HCl, and2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Part B: Preparation of2-(2,4-dihydroxy-6-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

The above complex mixture was heated to about 60° C. To the mixture wasadded 1 eq of orcinol (5-methylresorcinol), and the reaction mixture washeated to 80° C. to 85° C. for 8 h. HPLC analysis indicated almostcomplete conversion of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine leading to theformation of2-(2,4-dihyroxy-6-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Comparative Example 70 Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine complex withaluminum chloride without concentrated HCl

A mixture of 1 eq of isolated2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 3 eq of aluminumchloride in o-dichlorobenzene was stirred at room temperature for about5-6 h. The reaction mixture turned slightly yellow and was notorange-red as in the preceding example, indicative of a lack of the newcomplex formation from2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Example 71 Preparation of Reaction Facilitator From Aluminum Chlorideand Concentrated HCl

To a stirring mixture of 3 eq of aluminum chloride in o-dichlorobenzenewas added concentrated HCl (6 wt % based on aluminum chloride). Thereaction mixture was stirred at room temperature. The formation of a newoff-white mixture of the reaction facilitator was observed, which didnot change its color even after stirring at room temperature for 2 h.

Example 72 Preparation of 2,4,6-trichloro-1,3,5-triazine (cyanuricchloride) complex with reaction facilitator prepared from aluminumchloride and concentrated HCl

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in o-dichlorobenzene was added concentrated HCl (13 wt % basedon cyanuric chloride). The reaction mixture turned brownish-red after 30minutes of stirring at room temperature. The reaction became dark brownafter an additional 1 h of stirring at room temperature. The color ofthe reaction mixture indicated the formation of a new complex betweencyanuric chloride and the reaction facilitator prepared from aluminumchloride and concentrated HCl.

Comparative Example 72 Preparation of 2,4,6-trichloro-1,3,5-triazine(cyanuric chloride) complex with reaction facilitator prepared fromaluminum chloride without concentrated HCl

A mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride ino-dichlorobenzene was stirred at room temperature for 3 h. No change incolor from original off-white was observed, indicating lack of a similarcomplex formation of cyanuric chloride as in the preceding example,where cyanuric chloride was treated with the reaction facilitatorconsisting of aluminum chloride and concentrated HCl.

Example 73 Preparation of2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using Aliquat-336

To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminumchloride in benzene at about 0° C. was added Aliquat-336(tricaprylylmethylammonium chloride) (50 wt % based on aluminumchloride). A reaction with aluminum chloride was observed withtemperature increase. The reaction mixture was stirred at roomtemperature for 30 minutes, leading to the formation of a clearorange-red solution. To the resulting complex of cyanuric chloride withreaction facilitator was added 1.9 eq of m-xylene and the reactionmixture was stirred at room temperature for 1 h. HPLC analysis indicatedalmost 90% cyanuric chloride conversion to2-chloro-4,6-(2,4-dimethylphenyl)-1,3,5-triazine as the major productand 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine as the minor product,formed in a ratio of 3:1.

The invention described and claimed herein is not to be limited in scopeby the specific embodiments herein disclosed, since these embodimentsare intended as illustrations of several aspects of the invention. Anyequivalent embodiments are intended to be within the scope of thisinvention. Indeed, various modifications of the invention in addition tothose shown and described herein will become apparent to those skilledin the art from the foregoing description. Such modifications are alsointended to fall within the scope of the appended claims.

1. A process for synthesizing a triazine compound of Formula I:

wherein Ar₁ and Ar₂ are the same or different, and each independently isa radical of a compound of Formula II:

wherein R₆, R₇, R₈, R₉, and R₁₀ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbonatoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbon atoms, OR, NRR′, CONRR′, OCOR, CN, SR, SO₂R,SO₃H, SO₃M, wherein M is an alkali metal, R and R′ are the same ordifferent and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkylof 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24carbon atoms, or aracyl of 6 to 24 carbons atoms, and optionally witheither of R₆ and R₇, R₇ and R₈, R₈ and R₉, or R₉ and R₁₀, taken togetherbeing a part of a saturated or unsaturated fused carbocyclic ringoptionally containing O, N, or S atoms in the ring, which comprises:simultaneously reacting in the presence of a reaction facilitatorcomprising at least one Lewis acid and at least one reaction promoter,sufficient amounts of a cyanuric halide of Formula V:

where each X is independently a halide such as fluorine, chlorine,bromine or iodine, with a compound of Formula IV:

wherein R₁, R₂, R₃, R₄, and R₅ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbon atoms, OR, NRR′, CONRR′, OCOR, CN, SR, SO₂R,SO₃H, SO₃M, wherein M is an alkali metal, R and R′ are the same ordifferent and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkylof 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24carbon atoms, or aracyl of 6 to 24 carbon atoms, optionally with eitherof R₃, and R₄, or R₄ and R₅, taken together being a part of a saturatedor unsaturated fused carbocyclic ring optionally containing O, N, or Satoms in the ring, and Y is a direct bond, O, NR″, or SR″ wherein R″ ishydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbonatoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms,acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms,cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, oraracyl of 6 to 24 carbon atoms, and a compound of Formula II:

wherein R₆, R₇, R₈, R₉, and R₁₀ are the same or different and each ishydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbonatoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms,aracyl of 6 to 24 carbon atoms, OR, NRR′, CONRR′, OCOR, CN, SR, SO₂R,SO₃H, SO₃M, wherein M is an alkali metal, R and R′ are the same ordifferent and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkylof 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24carbon atoms, or aracyl of 6 to 24 carbon atoms, and optionally witheither of R₆ and R₇, R₇ and R₈, R₈ and R₉, or R₉ and R₁₀, taken togetherbeing a part of a saturated or unsaturated fused carbocyclic ringoptionally containing O, N, or S atoms in the ring, for a sufficienttime, at a suitable temperature and pressure, optionally in the presenceof at least one solvent, to form the compound of Formula I, with theproviso that: (1) said reaction promoter is different from the reactantwhich is reacting in that step, and (2) the compound of Formula II isdifferent from the compound of Formula IV.